The world number one extended his record this year to 18-0 as he triumphed 6-3 6-4 in one hour and 18 minutes on Saturday.
Djokovic added the ATP 500 title to his victory at the Australian Open, which had followed his role inspiring Serbia to glory at the inaugural ATP Cup.
After saving three match points against Gael Monfils in the semis, the Serbian relished his 79th Tour title as Tsitsipas lost in the final for the second straight year, having been beaten by Roger Federer last season.
Djokovic was playing in Dubai for the first time since 2016 and had not won the event since his fourth success seven years ago.
Tsitsipas came into the match in form having built on his Open 13 Marseille triumph with a strong run to the final and he forced the first break point in the fifth game, though he could not convert.
A wide backhand from the Greek as he served at 3-4 gave Djokovic his first opportunity and the 17-time major champion seized it with a brilliant sliding backhand pass, before claiming the set with backhand down the line in the next game.
Top seed Djokovic built a 0-30 lead in the opening game of the second set only for Tsitsipas to halt his momentum with what looked like a key hold.
The players exchanged breaks when Djokovic moved 3-2 up only for his opponent to strike straight back, the Serbian sending a forehand long moments after the Greek had come out on top in a 25-shot rally.
But the more experienced player delivered when it mattered most, forcing two chances at 4-4 and taking the first when a Tsitsipas backhand found the net.
Djokovic had few problems serving it out, quickly earning three match points and needing just one as a backhand winner led to him embracing Tsitsipas before letting out a passionate celebration on court as his fantastic form continued.
The world number one eased to a 6-1 6-2 triumph over Tunisian veteran Jaziri in a contest lasting one hour.
Djokovic and Jaziri had met once before in their careers, with the Serbian defeating him by an identical scoreline at the same tournament back in 2016.
Three weeks on from his dramatic five-set win over Dominic Thiem in the Melbourne final, Djokovic did not have to defend a single break point and converted four of his eight opportunities in a display that saw him hit 22 winners.
He raced into a 5-0 lead in the first set and while Jaziri – ranked 260 in the world – was marginally more competitive in the second, Djokovic sprinted to victory after breaking at 2-2, converting his first match point with his seventh ace.
"It's a great way to start out the tournament," said Djokovic. "I think I've done everything as well as I imagined it could be for the first match.
"Of course, there's things that always can be improved, things that can be better. But I have to be satisfied with the performance."
Elsewhere in the ATP 500 event on Monday, there were wins for Russian duo Karen Khachanov and Andrey Rublev.
Khachanov won 7-6 (7-2) 6-1 against Mikhail Kukushkin, while Rublev battled to a 6-4 6-4 triumph over Italian qualifier Lorenzo Musetti.
Richard Gasquet secured a hard-earned 7-6 (7-5) 6-4 victory in his contest with Lloyd Harris, while Philipp Kohlschreiber booked a round-two meeting with Djokovic when he recovered from losing the first set to eliminate wildcard Mohamed Safwat.
A teenager going places, Spaniard Alcaraz was set to shoot up to a career-high ranking inside the ATP top 20 on Monday on the strength of his successful week in Brazil.
He was too strong for Argentina's Diego Schwartzman in what turned out to be a one-sided final, with Alcaraz a 6-4 6-2 winner over an experienced and classy opponent.
It made him the youngest winner of an ATP 500 tournament, since the 2009 creation of that category. Such events rank below the importance of the Masters 1000 tournaments but remain prestigious, and it is one step at a time for now for Alcaraz towards lofty targets.
Alcaraz said: "My ambitions are to be number one in the world, a winner of grand slams, a winner of Olympic medals... I am a boy who dreams big."
This clay-court success whets the appetite for what Alcaraz might achieve on the surface over the coming months. He won the Umag tournament in Croatia on clay last July but will likely be targeting the likes of Rome, Barcelona, Madrid, Monte Carlo and even Roland Garros for similar success this year.
It was in Rio two years ago that Alcaraz first won an ATP main-draw match.
"Two years later, winning the tournament means a lot to me," Alcaraz told a news conference. "When I came here for the first time, I came to continue enjoying myself, to learn from the best. This time I had high expectations and I came thinking that I could win, that I am a candidate.
"I am super happy to have won my first ATP 500. It has been a week full of emotions and to be able to win this final has been a great joy for me."
Alcaraz was gutted to miss last year's Davis Cup finals after testing positive for COVID-19, but the powerful teenager is on a mission to maximise his talent in 2022.
He went toe to toe with Matteo Berrettini in the third round of the Australian Open, coming from two sets down to force a decider against last year's Wimbledon runner-up, only to lose out on a tie-break.
This time, Berrettini was among his victims on the road to the title in Rio.
Alcaraz said after Sunday's win, according to Spanish newspaper AS: "The expectations that people have of me are high, and I appreciate that they see that I can be the best in the world, but both my team and I know how difficult it is.
"I think I'm on the right path and if I don't deviate from it and keep doing things well, it won't be guaranteed, but I will have opportunities."
The world number 25 retired from his opening round match with Casper Ruud on Wednesday when a set and break down.
He was competing in his second tournament since withdrawing from the US Open with a positive COVID-19 test in August, having also fallen at the first hurdle at last week's Internazionali d'Italia.
Speaking after his exit in Germany, Paire revealed he had been self-isolating in his hotel room in the lead up to the match and was only allowed to practice for one hour but was still given the green light to compete.
"I spent 10 days in a hotel room during the US Open and again now," he said. "I am tired. I practiced for one hour and then went to the hotel room - it is impossible to do. I was tired and had to stop.
Asked to clarify if he tested positive again during his time in Hamburg, Paire replied: "Yes, I was positive here in Hamburg since I arrived. The only negative test I got was yesterday.
"Before that, there was two in a row where I was positive. But the rules seem different here. The ATP has to explain what the rules are. In Paris right now, players are testing negative, but because the coach is positive, they cannot play.
"Here in Germany, you test positive and can play. So again thank you to the tournament and the doctor here in Hamburg for letting me play. There are some rules I obviously don't understand too much.
"I was negative after the US Open, negative in France, negative in Rome and then positive in Hamburg. That's all I know.
"It's tough for me to understand when I arrive here in Hamburg and they tell me to stay in my room again. I really don't understand. Honestly, it is not easy for me."
Paire is due to take part in the French Open, his home grand slam, which begins on Sunday.
Paul edged the third seed 6-3 6-7 (2-7) 7-6 (7-2) in three hours and 29 minutes in their semi-final clash in Acapulco.
World number 23 Paul actually generated a match point late in the second set but spurned his initial chance, then waiting another two hours before winning in the third-set tie-break.
Paul let match point slip at 5-4 in the second set and had to rally back from 3-1 down in the third, but triumphed on his fourth match point.
"I couldn't be happier," Paul said. "The goal for this year was to get the ranking up and get more trophies. I only have one trophy on Tour between singles and doubles.
"You don't get trophies unless your in the final, and hopefully I can play another good match tomorrow and get the winner's trophy."
The 2023 Australian Open semi-finalist will take on Alex de Minaur in Saturday's decider, after he defeated Holger Rune 3-6 7-5 6-2 in two hours and 50 minutes.
In the Chile Open, local Nicolas Jarry progressed into the semi-finals with a 3-6 6-3 6-4 win over German qualifier Yannick Hanfmann. Jarry will face Spaniard Jaume Munar after he won 6-3 3-6 6-2 over Thiago Monteiro.
Third seed Sebastian Baez got past Laslo Djere 7-6 (7-4) 6-4, setting up a semi-final date with Tomas Martin Etcheverry after he won 6-1 6-2 over Dusan Lajovic.
Peniston beat world number five Casper Ruud as he reached the quarter-finals at the Queen's Club Championships last week, and followed that up by recovering from a set down against Rune to reach Eastbourne's last 16 in impressive fashion.
After wrapping up a 4-6 7-6 (7-5) 6-1 win, the 26-year-old told the home crowd: "I'm very happy with that. A tough start but I managed to fight, thanks to you guys.
"Since Queen's it has been madness. A couple of weeks ago was a lot different and things have changed, but I'm loving it."
Rune, who was twice two points from victory in an enthralling contest, was jeered by spectators after hitting a ball out of court and kicking his towel bin after being broken in the third set.
Peniston will face Pedro Martinez in the next round after he benefited from fellow Spaniard Alejandro Davidovich Fokina being forced to retire at one set apiece, while Ugo Humbert fell to a 6-7 (2-7) 6-3 6-4 reverse against Brazil's Thiago Monteiro.
Lorenzo Sonego posted a 4-6 7-6 (7-5) 7-6 (7-1) win over James Duckworth, while Tommy Paul recovered from a set down to beat Francisco Cerundolo and home favourite Dan Evans overcame Adrian Mannarino 6-4 6-3.
The seeds in action at the Mallorca Open endured mixed fortunes as Sebastian Baez cruised past Jordan Thompson in straight sets, but Botic van de Zandschulp was beaten by Marcos Giron.
The Dutchman succumbed to a 6-7 (6-8) 6-4 7-6 (7-2) defeat, while Germany's Daniel Altmaier beat Dusan Lajovic 7-5 7-6 (7-2).
Nick Kyrgios set up an enticing last-16 meeting with fifth seed Roberto Bautista Agut by knocking out Serbia's Laslo Djere in a marathon three-set contest, recovering to win 5-7 7-6 (7-1) 7-6 (7-1).
The Austrian was one set away from winning his first grand slam title in Melbourne, only for Djokovic to edge a thrilling encounter 6-4 4-6 2-6 6-3 6-4.
After two weeks to recover from what Thiem acknowledged was a tough defeat to take, the world number four is reflecting positively and looking forward to playing again as top seed at the Rio Open.
Thiem starts his campaign against home hope Felipe Meligeni Alves on Tuesday and is the only top-20 player taking part in the ATP 500 event.
"Coming on clay is like coming home," Thiem, a 2017 winner in Rio, said to the ATP Tour. "I like the surface and also really like South America. It's a completely different atmosphere.
"I've had great experiences, won here, won Buenos Aires twice, so it's very easy for me to come back here."
Of his Australian Open exploits, Thiem added: "I feel great about the performance in Melbourne. It was a hell of a two weeks, beating three top-10 guys and then losing to Novak Djokovic 6-4 in the fifth.
"Of course, it was a huge disappointment. But after some time to reflect, it was a great tournament and start to the season. I hope to keep that good form going."
At a period of the season where hard-court tournaments return to the schedule in Indian Wells and Miami next month, Thiem is not worried about his momentum being disrupted.
He said: "For me, it's no problem to play on clay for one or two weeks and then switch back to hard courts."
The world number nine beat British hope Cameron Norrie 6-4 6-7 (5-7) 6-3 in the London showpiece match on Sunday, setting himself up ideally ahead of a Wimbledon mission later this month.
Whereas Becker was 17 when he triumphed at Queen's Club in 1985, going on to be champion at Wimbledon just weeks later, Berrettini is 25 years old and established as a leading player.
His big serve – an aspect of his game he shares with vintage Becker – proved a huge asset against Norrie as Berrettini served 19 aces and won 91 per cent of points when landing his first delivery.
Norrie could not forge a break point but did commendably well to force a deciding set in a match that lasted three minutes short of two hours.
Berrettini said he had experienced an "unbelievable week", lifting his first title at ATP 500 level, and he was blown away by the Becker link.
"If I think about his name and my name, it's crazy," he said in an on-court interview.
"I was dreaming about playing this tournament. I was watching when I was a kid and now I had the chance to lift the trophy. It's a dream come true."
Berrettini could be a threat to anyone if his serve fires at Wimbledon, and he was proud of how he fended off Norrie.
"I didn't check the numbers during the match. I knew I was serving well," said Berrettini. "I knew it was important because in the rallies this guy is dangerous. I knew I had to play my best tennis."
Berrettini said his celebrations were likely to be muted, given he is in a pre-Wimbledon bubble, predicting his team would limit his post-match treats to "probably room service and sparkling water".
There would be cause for greater cheer if Berrettini goes on a run at the All England Club, with Wimbledon due to begin on June 28. His previous best performance at Wimbledon was a run to the fourth round two years ago.
Berrettini told Amazon Prime: "I know it's going to be a really tough tournament.
"Probably all the players have extra motivation to play well there so it's going to be tough, but I have a lot of confidence."
Following a quarter-final exit to Dominic Thiem at the Australian Open that saw him lose the world number one ranking, the Spaniard earned his third Acapulco title without dropping a set.
Nadal saw off Taylor Fritz 6-3 6-2 in the final of the ATP 500 event for his 85th Tour-level title and first of 2020, taking momentum from his enjoyable spell in Mexico.
"After not competing since Australia, it's an important week for me and an important moment," said the 33-year-old.
"I couldn't be happier. I played a great event from the beginning to the end. I played solid, with the right intensity, the right passion and my forehand worked well.
"This title doesn't mean that I will have a great season. It means another good start. It gives me confidence and allows me to be in a privileged position in the ATP Race [To London].
"I am always happy after playing here. Now imagine how I am after getting the title!"
Nadal's success came as rival Novak Djokovic also won this week, claiming a 6-3 6-4 victory over Stefanos Tsitsipas in the final of the Dubai Tennis Championship.
Djokovic has an 18-0 record this season having won the ATP Cup with Serbia and followed that up with the Australian Open and his fifth crown in Dubai.
He joked about going the whole of 2020 unbeaten in his on-court interview and laughed it off again in a later discussion with reporters while explaining his determination to continue the hot streak.
"Of course, I'm trying to embrace the moment and appreciate where I am," Djokovic said.
"This has been one of the best starts of all seasons I had in my career. It has started in the most perfect way possible.
"I am aware, most of the matches that I'm going to play, the players will not have much to lose. They will go out and try to play their best and stop the streak.
"At the same time, the more I win, the more confident and comfortable I feel. I'm just grateful that I'm playing well, feeling well. I've won many matches now in a row. I'll try to keep that run going."
Nadal and Djokovic are both scheduled to return to action in Indian Wells for the first Masters 1000 event of the season from March 12.
Auger-Aliassime won his first Tour-level title at the event last year and went from strength to strength in 2022, winning another three singles trophies.
The world number eight, seeded third, started his title defence with a convincing 6-2 6-3 defeat of Italy's Lorenzo Sonego on Tuesday.
"Of course, I was hoping to win and get through, but 6-2, 6-3 is a great performance against a player that is tricky like he is... it's a great way to start the week," said Auger-Aliassime, who needed just 82 minutes to clinch victory and set up a last-16 meeting with qualifier Gregoire Barrere.
The Canadian is relishing his title defence, and feels he is a stronger competitor than this time last year in a warning shot to his rivals.
He added: "Last year was an amazing year, but this year is a different one. I think I'm a better player overall.
"Of course, the best thing I can do compared to last year is win again, so hopefully I can do that. The draw is really strong, but I'm confident if I can keep playing the way I did today I'll get my chances and then we'll see."
Auger-Aliassime might be the reigning champion, but world number three Tsitsipas is the favourite.
Emil Ruusuvuori was no match for Australian Open runner-up, who prevailed 7-5 6-1 and has a 13-1 record for the season.
"The process that you get to repeat these things over and over again, it gives you tremendous understanding of how things actually work," Tsitsipas said.
"I think being able to get in these moments more and more often on the Tour helps you understand, makes you wiser when you're trying to deal with all these problems."
Tsitsipas, who could face Open Sud de France champion Jannik Sinner in the next round, ensured there would be no curse of the top seed in Rotterdam, where the favourite had lost their first match in two of the last three editions.
On both occasions (2020 and 2021), that was Medvedev, but the former world number one fought from a set down to beat Alejandro Davidovich Fokina 4-6 6-2 6-2.
World number 10 Hubert Hurkacz also had to battle against a Spaniard in the form of Roberto Bautista Agut. The fifth seed needed three hours to win 7-5 6-7 (7-9) 7-6 (7-4) and tee up an encounter with Grigor Dimitrov.
Alexander Zverev defeated Soonwoo Kwon in straight sets to book his progress, while Gijs Brouwer got the better of Marc-Andrea Huesler.
Rain wreaked havoc in Rio, where only two quarter-final matches were completed at the ATP 500 tournament on Friday.
Thiem's back is against the wall, with the Australian Open runner-up and world number four down 7-6 (7-5) 2-1 against Mager – who is featuring in his first ATP Tour quarter-final.
Lucky loser Attila Balazs and qualifier Pedro Martinez were also playing when the rain returned in Brazil, with the latter leading 6-2 2-2.
Cristian Garin managed to win through to the semi-finals after the third seed claimed his seventh successive victory by rallying past Federico Coria 2-6 6-3 7-5.
Next up for Garin is fifth seed Borna Coric, who defeated Lorenzo Sonego 7-6 (7-5) 6-3 on the Brazilian clay.
At the Delray Beach Open, second seed Milos Raonic and fellow big server Reilly Opelka will meet in the semi-finals.
Raonic beat Steve Johnson 7-6 (8-6) 6-3 and 2019 New York Open champion Opelka took down Kwon Soon-woo 6-3 6-4 at the ATP 250 event.
"It's going to be tough. He gets a lot of free points on his serve and you've got to make him play," Raonic said.
"You can't just make him play though because he goes for it from the centre of the court. You've got to move in, you've got to find a way to be aggressive."
Elsewhere, Yoshihito Nishioka overcame teenager Brandon Nakashima 3-6 7-6 (7-5) 6-4 and sixth seed Ugo Humbert eased past 2018 winner Frances Tiafoe 6-1 6-2.
After lifting trophies in Umag, Rio de Janeiro and Miami over the last nine months, Alcaraz landed a first in Spain, his homeland, by fighting off compatriot Pablo Carreno Busta.
The 18-year-old scored a 6-3 6-2 victory in the final, having earlier in the day edged out Alex De Minaur 6-7 (4-7) 7-6 (7-4) 6-4 in a semi-final lasting three hours and 39 minutes.
Alcaraz has been listening to music from the Rocky boxing movies before his matches, notably the classic Eye Of The Tiger from Rocky III.
"I try to listen to that song before every match. It motivates me," he said on Amazon Prime. "When I listen to the music I remember the movie, and it's amazing this big fight that Rocky has and everything that he is trying to have, that experience in every match, and that's what motivates me."
It was already known that Alcaraz would enter the top 10 in the rankings for the first time on Monday, and he is set to go to ninth on that list, with many expecting him to eventually go all the way to the top.
Alcaraz will be the first teenager to enter the top 10 since Andy Murray in 2007, and the youngest since Rafael Nadal moved into the elite pack in April 2005 after winning in Barcelona.
The semi-final involving Alcaraz and De Minaur, and the last-four battle between Carreno Busta and Diego Schwartzman, had both been carried over into finals day, with each match tied at 2-2 in the opening set when rain stopped play on Saturday.
Carreno Busta scored a breezy 6-3 6-4 win over Argentinian Schwartzman and that looked to give the 30-year-old an advantage, but he found the teenage legs of Alcaraz still had plenty of life left in them for the final.
This was the first all-Spanish final in Barcelona since 2013, when Nadal beat Nicolas Almagro, and Alcaraz was clinical.
Carreno Busta drove a backhand wide on set point as Alcaraz took the opener, and the youngster broke for a 4-3 lead in the second set before picking apart Carreno Busta's serve to love to seal victory.
"It means a lot," Alcaraz said. "I've watched this tournament since I was a kid. I've always wanted to play and win this tournament."
Second seed Rublev was the latest scalp of Cerundolo's fine run of form, the Argentine making it seven consecutive wins by wrapping up a 6-4 6-2 success in just an hour and a half in Germany.
Having furthered his momentum with a second top-10 win in as many weeks, Cerundolo said: "It is the first time it has happened for me. I am playing against the top guys and I am playing well, it is unbelievable."
Cerundolo will face Aslan Karatsev in the last eight after he recovered from a set down to beat Daniel Elahi Galan 3-6 6-3 6-4.
World number six Alcaraz fared better than Rublev, registering a 7-6 (7-4) 6-3 win over Krajinovic to tee up a final-four meeting with Karen Khachanov, who beat Fabio Fognini in straight sets.
Meanwhile, a host of big names including Casper Rudd and Matteo Berrettini reached the last eight of the Swiss Open in Gstaad, as Dominic Thiem continued his revival with a win over Federico Delbonis.
Thiem reached his second quarter-final in as many weeks with an impressive 7-6 (8-6) 6-3 triumph despite letting a 5-2 lead slip in the opener, registering his first tour-level straight-sets victory since May 2021.
Having set up a meeting with Juan Pablo Varillas, the 2020 US Open champion beamed: "I have won two matches which means a lot to me right now, I really need those ranking points. Every match win is something very special."
The Austrian will be joined in the next round by first and second seeds Ruud and Berrettini, who eased past Jiri Lehecka and Richard Gasquet respectively.
Spanish duo Albert Ramos-Vinolas and Pedro Martinez also both progressed to the last eight despite dropping a set, with the latter setting up an enticing clash with Berrettini on Friday.
Rublev trailed Denis Shapovalov by a set but fought back to prevail 4-6 6-3 6-4 and ensure there will be a home hope in the final.
He saved five of six break points in the process of earning victory over the Canadian, the win moving Rublev ahead of Diego Schwartzman into eighth place in the battle to qualify for the season-ending tournament in London.
His opponent will be 2019 finalist Coric, who will be looking to go one better than last year after he staged a turnaround of his own.
Coric, beaten by Daniil Medvedev in his previous appearance in the final, saw off Milos Raonic 1-6 6-1 6-4.
Alexander Zverev progressed to his second final since the resumption of the ATP Tour at the Cologne Indoors.
Zverev overcame Alejandro Davidovich Fokina 7-5 7-6 (7-3) but was full of praise for the NextGen ATP Finals contender.
"He played much better tennis and I think he's somebody who is going to go up the [FedEx ATP] Rankings very quickly," Zverev said.
"For me he's a great guy as well. He's very talented, extremely good with the hands. I think he's somebody who's going to find his way up and it's going to be interesting to see what the future weeks [hold for him] this year and next year as well."
The German will meet Felix Auger-Aliassime, who recorded a 6-3 1-6 6-3 triumph over Roberto Bautista Agut.
At the Sardegna Open, Marco Cecchinato routed Danilo Petrovic 6-1 6-0 and will face Laslo Djere in the final after Lorenzo Musetti retired in the third set with a right elbow injury. Djere was leading 2-6 6-2 4-1.
The Russian wrapped up the win at the Wiener Stadthalle in an hour and 19 minutes on Sunday as he clinched his fifth ATP title of the season.
Unheralded Sonego, ranked at number 42 in the world, had reached the final in the wake of a shock quarter-final win over world number Novak Djokovic but could not repeat the feat against a clinical Rublev.
"This tournament is really special for me because my grandma was also Austrian, so I have Austrian blood," Rublev said during the trophy presentation.
Italian Sonego found no way past Rublev's serve as he failed to inflict a single break.
It ensured Rublev ended the tournament without once surrendering his serve in 38 games – becoming the first player to achieve the feat in an ATP tournament since Alex de Minaur reeled off 42 games at Atlanta in 2019.
Having made headlines after his semi-final triumph over Hubert Hurkacz by writing "no war please" on a television camera in protest at Russia's invasion of Ukraine, Rublev wrapped up his third title in just a matter of days in emphatic fashion, after winning both the singles and doubles titles at the Open 13 Provence in Marseille last week.
The Russian world number seven had needed three sets in each of his last three contests but wrapped up a more straightforward victory against his Czech opponent, who had defeated 20-time Grand Slam champion Novak Djokovic en route to the final.
Rublev broke Vesely's serve in the fourth game of the contest, not dropping a single point behind his first serve as he roared to a 6-3 win in the opening set.
The 24-year-old then broke again in the opening game of the second set, before the Czech, ranked number 123 in the world, battled back bravely to level the set at 3-3.
Rublev responded in brutal fashion, however, immediately breaking again and going on to seal a comfortable victory, hitting just eight unforced errors throughout the contest, as he claimed his 10th career title.
The victory made it 13 match wins in a row for Rublev across singles and doubles after his successful time in Marseille, where he successfully teamed up with Ukrainian Denys Molchanov for a symbolic doubles triumph.
"I was lucky today, and that's why I am happy to be the champion, I didn't expect this," said Rublev. "It's an amazing feeling and I don't know what to say."
Tsitsipas has himself enjoyed a fine start to the year, reaching the semis of the Australian Open, but it was Rublev who progressed to the final in more routine fashion than might have been expected.
He prevailed 6-3 7-6 (7-2), marking his 12th win from 13 matches this season.
The victory also extended his winning streak in ATP 500 matches to 19. Only Roger Federer (28) and Andy Murray (21) have produced longer such runs.
"[I play tennis] to play at the best level, to play at the best tournaments, to try to compete, then to go deep and to try to win them," Rublev said in an on-court interview. "A final is always special, so I am going to try to do my best tomorrow [Sunday]."
Rublev is likely to require his best given the form Marton Fucsovics, his opponent, is in.
Fucsovics came through qualifying to reach the main draw and delivered a superb performance to stun world number 26 Borna Coric 6-4 6-1.
The final will be the third of Fucsovics' career and his first since February 2019, when he lost to Rublev's Russian compatriot Daniil Medvedev at the Sofia Open.
The fifth seed found a crucial break of serve when leading the opener 5-4 to take the first set in Kazakhstan, before winning the next three games to put himself in the ascendancy in the second.
And despite a desperate last stand to stay in the match from Djere, Rublev held serve three times with relative ease to finish off his Serbian opponent.
Eighth seed Felix Auger-Aliassime served 14 aces to Roberto Bautista-Agut's two in their first-round match, but it was the Spaniard who advanced with a 6-4 7-6 (8-6) success.
Meanwhile, world number 10 Hubert Hurkacz overcame Francisco Cerundolo in straight sets.
Adrian Mannarino, the runner-up in Astana in 2020, came from a set down to beat Stan Wawrinka – playing as a wildcard – 1-6 6-2 6-3, and qualifier Zhizhen Zhang romped to victory with a superb third set to seal a 4-6 6-4 6-1 comeback win of his own over Aslan Karatsev.
At the Tokyo Open, fourth seed Frances Tiafoe cruised into the second round with a 6-3 6-4 triumph over Yasutaka Uchiyama, one of three Japanese players who crashed out at the first-round stage of their home tournament.
Uchiyama's countrymen Taro Daniel and Shintaro Mochizuki also tasted defeat at the hands of Bernabe Zapata Miralles and Brandon Nakashima, respectively.
Second seed Rublev won this event two years ago but there will be no such run this time around after his 6-4 6-4 loss on Wednesday.
De Minaur broke the world number five early in each set and sealed the win at the first time of asking, moving to a 3-0 head-to-head record against Rublev on hard courts.
The Australian will face Maxime Cressy in the next round, who bounced back from his Open Sud de France final defeat by beating Tim van Rijthoven.
Jannik Sinner saw off Cressy in that Montpellier showdown and the Italian carried that form into this tournament, though he needed three sets to overcome Benjamin Bonzi.
Frenchman Bonzi forced a decider but Sinner regained his composure in the final set to prevail 6-2 3-6 6-1 and set up a heavyweight clash with top seed Stefanos Tsitsipas.
There was no such progress for Alexander Zverev, who joined Rublev in suffering an early exit.
The German came unstuck 4-6 6-3 6-4 to home favourite Tallon Griekspoor, whose four wins over top-20 opponents have all come in Rotterdam.
Stan Wawrinka, the champion in 2015 and runner-up four years later, will face the winner of that tie, after he beat Richard Gasquet 6-3 6-3 to reach the quarter-finals.
Holger Rune reached the semi-finals in Montpellier, and like Sinner the fourth seed progressed into round two, claiming a routine straight-sets victory over qualifier Constant Lestienne.
"It was tricky. It's a lot about finding the rhythm here in the beginning of the tournament and first match you have to really be on your toes, especially I played a qualifier today who already has two matches in his bag," Rune said.
"It made it more difficult, but I'm happy how I handled every situation today."
Hubert Hurkacz was another seed to fall out, with the world number 10 going down 7-6 (7-4) 7-6 (7-5) to Grigor Dimitrov.
The appetising showdown between Rublev and former world number one Murray was handed a primetime evening slot on Wednesday's schedule by tournament organisers, given the appeal of a clash between one of the ATP Tour's brightest younger stars and the three-time grand slam winner.
World number eight Rublev is, at the age of 23, among the band of players who have emerged as potential torchbearers for the men's tour once the likes of Murray and the big three of Roger Federer, Rafael Nadal and Novak Djokovic make way.
After wildcard Murray's win over Robin Haase on Monday, Rublev secured victory on Tuesday against 80th-ranked Giron, who earned his place in the ATP 500 tournament through qualifying.
Murray and Rublev have played only once before, in entirely different circumstances to those surrounding Wednesday's match. That previous encounter came at the Australian Open in 2017, with Murray, then ranked number one in the world, scorching to a 6-3 6-0 6-2 win in round two.
The Scot has since undergone major surgery on a hip problem that has threatened to end his career, and heads into his clash with Rublev ranked 123rd in the world but eager to show he can compete at a high level.
"Andy is a true legend and I have a really good connection with him. I really like him as a person and as a player. He destroyed me once in the past. I'm sure we'll have great, long rallies and it will be a fight," Rublev said, quoted via the ATP website.
Australian Open semi-finalist Stefanos Tsitsipas passed his first-round test by scoring a narrow win over a player that beat Murray in Montpellier last week – the second seed and world number six overcoming Belarusian Egor Gerasimov 7-6 (7-4) 7-5.
The tournament lost a three-time grand slam champion when Stan Wawrinka was edged out 6-4 7-5 by Russian Karen Khachanov in a tough first-round matchup for the Swiss, who sits just one place above the Russian at number 20 in the world rankings.
Alex de Minaur beat fellow Australian John Millman 6-1 6-4, while top seed Australian Open runner-up Daniil Medvedev begins his challenge on Wednesday when he tackles Serbian Dusan Lajovic.
