Djokovic had started 2023 by coming out on top in all 15 of his matches and winning the Australian Open, with his overall winning streak standing at 20 games.
But Medvedev ended the world number one's perfect start to the year with a superb display to take a 6-4 6-4 triumph on Friday.
The 27-year-old, who himself made it 13 consecutive wins, broke Djokovic twice on the way to taking the opening set.
Medvedev's high standard of play continued in the second, breaking Djokovic in the first game before holding in all five of his service games to secure a straight-sets victory.
"When you play against Novak you just have to play your best," Medvedev said after the win. "Kind of hope he doesn't play his best on the day because when he plays his best, well he has 22 grand slams, so even if you play your best, it is going to be tough, not sure you win.
"I managed to play a higher level than him today. In the second set I didn't face one break point, but there were so many 30-30 games. But I managed to stay composed and I am happy to be in the final tomorrow."
His win means he will face countryman Rublev in the final after the reigning champion kept his hopes of retaining the title alive with a 6-3 7-6 (11-9) success over Alexander Zverev.
Rublev had never previously won a match or set against Zverev in five previous meetings, but won three of the German's service games in the opener to go a set ahead.
The second seed was out-aced nine to two in the second set but managed to force a tie-break, going on to survive a set point before eventually securing the win on his sixth match point.
Rublev will look to join Roger Federer and Djokovic as only the third repeat champion at the tournament when he takes on Medvedev in Saturday's final.
The compatriots have met six times previously with Medvedev winning four of them, though Rublev has taken victory in their last two match-ups.
Playing in his first tour-level final since winning the Mexico Open in August, Medvedev found himself on the back foot after Shapovalov came out on top in a 50-minute opener.
The world number four conceded serve twice in the first set – the first time he had been broken throughout his run in Austria.
However, Medvedev hit back to claim the second set at the first time of asking.
Having lost serve twice in the decider, Shapovalov hung on in to frustrate Medvedev, saving six match points before finally succumbing to a deft drop-shot that the Canadian could only clip back into the net.
The victory marks Medvedev's second title of 2022, while it also ensures the Russian – who worked his way to world number one earlier in the year – will play in the ATP Finals next month, after going for glory at the Paris Masters.
"This match was the best of the week because Denis was really playing unreal until probably 4-3 in the second set," said Medvedev, who is aiming for a strong end to the season.
"He dropped his level by maybe two per cent and I was able to use it. This is one of the best victories when you know your opponent is on top of you, but you try and stay there and do what you can.
"I like to play indoor hard courts at the end of the season. I feel that I do a great job with my team not to arrive burnt out.
"I'm looking forward to the last two tournaments of the year which are really important and I usually play well."
Medvedev, who has reached two hard-court grand slam finals, as well as winning last year's ATP Finals, has never been beyond the last four on grass. He has only done so once on clay.
The Russian will get another chance on Friday, though, against Pablo Carreno Busta.
That is his reward for beating Casper Ruud, who Medvedev acknowledged likely also does not favour the grass season.
"I don't think grass is his best surface, but in the first set he was playing top level and I couldn't get any break points," Medvedev said after beating Ruud 7-5 6-1.
"But as soon as he started serving a bit worse and making some errors, I tried to use it as fast as I could.
"It was important to win the first set and not in a tie-break, this gives me a boost of confidence."
Carreno Busta defeated Jordan Thompson in straight sets but was not followed into the semis by either of the other Spaniards in action.
Third seed Roberto Bautista Agut was toppled by Sam Querrey, as Feliciano Lopez lost to Adrian Mannarino.
At the Viking International in Eastbourne, there is an Australian in each semi-final after wins for Alex de Minaur and Max Purcell.
De Minaur wore down Vasek Pospisil 6-4 6-4 and now faces Kwon Soon-woo, who was similarly comfortable against Ilya Ivashka.
Purcell battled past Andreas Seppi, recovering from a tough second set in which he succumbed 6-1, but must now face another Italian.
Third seed Lorenzo Sonego secured his semis spot by blasting past Alexander Bublik 6-1 7-5.
The world number one struggled to get going and repeatedly took his anger out on coach Gilles Cervara, who stormed out of his seat early in the second set.
Top seed Medvedev had already lost the first set 6-1 by that point and only fared slightly better in the second, which ended 6-4 in Hurkacz's favour.
Hurkacz has now won five ATP Tour titles, with this his first on grass, while Medvedev remains stuck on 13 having lost all three finals he has competed in this season.
The most recent of those losses came at the hands of world number 106 Tim van Rijthoven last week, but Medvedev had not dropped a set en route to Sunday's clash in Halle.
Indeed, Medvedev was 14-2 on grass since a first-round exit at Halle last year, yet Hurkacz broke the Russian's first two service games and eased into a 5-0 lead.
Having successfully served out the opener, Hurkacz – who beat the same opponent in this year's Miami Masters – again broke Medvedev in the first game of the second set.
Medvedev took aim at his coach at that point, with Cervara then spotted leaving the stands and failing to return for the remaining nine games, which went the way of the serve.
After easily navigating his way past Medvedev in a match lasting just over an hour, fifth seed Hurkacz becomes the seventh male player in the Open Era to win his first five career finals.
Former world number one Medvedev won 6-2 6-2 in an hour and eight minutes, adding to recent victories in Rotterdam and Doha as he extended his winning streak to 14 matches.
It gave him a tour-leading 19th match win of the season, edging ahead of Britain's Cameron Norrie, and means Medvedev will vault above Rublev to reach sixth in the new ATP rankings.
Appearing in his 30th tour-level final, Medvedev picked up his 18th career title and improved his head-to-head advantage to 5-2 against his compatriot.
He broke serve in the first and seventh games to sweep through the opening set, serving out to love to clinch it, and Rublev, who was the defending champion, offered no greater resistance in the second.
After beating Novak Djokovic in the semi-finals, this was supremely clinical from Medvedev, setting him up for tilts at the Masters 1000 events in Indian Wells and Miami over the coming weeks.
"It's amazing," said Medvedev in an on-court interview, "because the start of the year was not perfect."
He lost in round three of the Australian Open to Sebastian Korda, but has put that January jolt firmly behind him.
"In tennis, when you don't win tournaments, you are always doubting, no matter what happens in practice," Medvedev said. "So I was doubting a lot and now it just feels better. I was really happy with these three weeks and I'm looking forward to the next ones.
"Sometimes you feel you're doing all the right shots and you're losing matches, and sometimes you kind of don't even think, just go it, go for some crazy stuff. A lot of shots this tournament were landing which were maybe not supposed to be, and when confidence is going sometimes that helps a lot."
Medvedev's win makes him the third player in the last two years to land three titles in as many weeks, the ATP said, after Casper Ruud in July 2021 and Felix Auger-Aliassime.in October 2022.
The Russian top seed won 3-6 6-3 6-0 on Wednesday, having lost at the first hurdle in Hamburg and at the French Open prior to this ATP 500 event.
Medvedev fired in 22 aces to just three double faults and converted four of his six break points against Gasquet, who had also suffered an early exit at Roland Garros.
World number six Medvedev, the winner of this tournament last year, will face American Reilly Opelka next after winning in 97 minutes.
Opelka was also involved in a battle, recording 26 aces as he eventually saw off qualifier Nino Serdarusic 3-6 7-6 (7-5) 6-2.
Second seed Denis Shapovalov is through, too, having had a more comfortable outing in his 6-2 6-3 win over Viktor Troicki to book a last-16 tie against Ilya Ivashka.
Shapovalov converted all four of his break points and only needed 62 minutes to progress.
"Always great to get the first win, especially against a player like Viktor," said Shapovalov. "We have had a lot of battles before and they have been really long matches, so I'm really happy to get a straight-sets win.
"Indoor tennis is just natural for me. It is what I grew up playing on. It is difficult to have those transitions really quickly from clay court to hard court, but we are having to adapt to these situations quickly now."
Stan Wawrinka, meanwhile, is already in the quarter-finals after ending the challenge of home hope Evgeny Donskoy with a 6-1 3-6 6-3 triumph.
At the Cologne Indoors tournament, sixth seed Hubert Hurkacz saw off Mischa Zverev to reach the quarter-finals with a 6-4 6-3 win, while Dusan Lajovic was one of three seeds to fall at the Sardegna Open.
Second seed Lajovic went down 6-4 7-5 to fellow Serbian Laslo Djere, with Lorenzo Sonego and Pablo Andujar also crashing out.
The world number one was forced to save a set point in a tight opener before rallying in a tie-break and sailing through the second set in a 7-6 (7-3) 6-3 win.
Despite falling to a shock defeat to Tim van Rijthoven in 's-Hertogenbosch last week, Medvedev is now 14-2 on grass since a first-round exit at Halle last year, and was delighted to make up for 2021's performance on one of his favoured surfaces.
"I didn't play well in Halle last year, so I'm happy that this year I managed to raise my level," he said after the win.
"As I've always said, I love playing on grass, so I'm happy to show to myself that I'm capable of being in the final of one of the greatest tournaments, especially on grass, and of course I'm looking forward to tomorrow."
Standing between Medvedev and the second grass-court title of his career is Hurkacz, who required two tie-breaks to edge a thrilling contest with Nick Kyrgios, winning 4-6 7-6 (7-2) 7-6 (7-4).
Elsewhere, last year's Wimbledon runner-up Matteo Berrettini remains on course for back-to-back titles at the Queen's Club Championships after a straight-sets win over Botic van de Zandschulp in the final four.
Berrettini overcame a rain stoppage to secure his eighth consecutive victory, securing a 6-4 6-3 win, and delighted after triumphing in challenging conditions.
"It was a really tough match. We stopped for the rain. I had a lot of chances. It was windy again and really tough to play, but I definitely think it was the best match of the week, so I am really happy and looking forward to the final," the Italian said.
Berrettini will face world number 48 Filip Krajinovic in Sunday's final, after the Serb cruised past 2014 US Open champion Marin Cilic 6-3 6-3.
World number five Medvedev was in action for the first time since his US Open semi-final defeat to eventual champion Dominic Thiem and the top seed in Hamburg was defeated in straight sets.
Humbert overcame Kevin Anderson and Fabio Fognini in straight sets at the Internazionali d'Italia last week and he claimed another impressive scalp – his first against a top-10 player – after an hour and 22 minutes.
The 22-year-old Frenchman ensured Medvedev did not enjoy his first match on clay since last year's French Open, and he will now face Jiri Vesely in the second round.
Reigning champion Nikoloz Basilashvili went down 6-4 6-3 to Roberto Bautista Agut, while third seed Gael Monfils bowed out with a 6-4 6-3 loss to Yannick Hanfmann.
Fognini came from a set down to beat Philipp Kohlschreiber, and Karen Khachanov rallied back from a double break down in the decider to progress at the expense of Jan-Lennard Struff.
Felix Auger-Aliassime downed Lorenzo Sonego 6-2 7-6 (7-2) and Cristian Garin got the better of Kei Nishikori in straight sets.
At the Queen's Club Championships, second seed Matteo Berrettini came from a set down to finally see off Denis Kudla, winning 3-6 7-6 (7-5) 6-4.
Defending champion Berrettini was troubled by the world number 82, and was just a tie-break away from suffering an upset, but the Italian came through as he belted down 22 aces in the match.
Berrettini faces Tommy Paul in the quarter-finals after the American beat Stanislas Wawrinka in straight sets, 6-4 6-1.
Ryan Peniston carried on from knocking out number one seed Casper Ruud by beating Francisco Cerundolo 6-0 4-6 6-4, setting up a last eight clash with Filip Krajinovic after he came from behind to defeat Sam Querrey 4-6 6-3 6-4.
A 5-7 6-2 6-2 win for Medvedev gave the 27-year-old Russian his first trophy of the year, extending his career head-to-head record to 5-0 against Sinner.
The run from Medvedev this week has secured his return to the top 10 in the rankings, with the former number one set to go up three places to number eight on Monday.
Victory came in sharp contrast to Medvedev's last two appearances at the tournament, when he suffered first-round losses in 2020 to Vasek Pospisil and in 2021 to Dusan Lajovic.
Medvedev said after his win: "Thanks to all members of my team who are with me no matter what: some tough moments, some good moments, and we continue growing.
"The last two times I played here were terrible, and I'm happy to make it better this year."
Medvedev and Sinner's past meetings had curiously all come on indoor hard courts, as this also did.
Sinner won a title last week at the Open Sud de France in Montpellier, so the 21-year-old was not wanting for confidence as he looked to finally register a win over Medvedev.
The Italian out-rallied Medvedev at the end of the first set to snatch the vital break, but he could not ride that momentum into the early stages of the second.
An early break went the way of 2021 US Open winner Medvedev, whose remarkable defence was a key factor as the comeback gathered steam.
A double fault from Sinner handed Medvedev a 4-1 lead and a double break, nudging the match towards the decider.
When it came, first blood went to Medvedev as Sinner netted a backhand to give up a break in the third game.
The Moscow man saved a break point in the next game to stay ahead, and that setback left Sinner sapped, his challenge fading as Medvedev maintained an impressively high level.
In-form world number nine Monfils triumphed at the Montpellier championship the previous Sunday and made it nine straight Tour wins with a 6-2 6-4 success this time.
Canada's Auger-Aliassime, on the other hand, is still waiting for his first senior career title and was never really in the contest as Monfils ended the week without dropping a set.
Playing his fourth Tour final after a trio of 2019 defeats, the 19-year-old made a nervous start and was required to rescue three break points in just the third game after some wayward initial work with the forehand.
Auger-Aliassime merely delayed the setback until his next service game, though, Monfils coming out on top for a 3-2 lead as the pair did battle at the net.
Following a brief Monfils scare, Auger-Aliassime went long when defending a third break opportunity next time out and slipped further behind, allowing the third seed to serve out the opener.
There was no improvement from the Canadian when the match resumed, the second set beginning with a series of errors and a crushing break to love.
Monfils stylishly got the better of an apparently defeated Auger-Aliassime at the net to tee up another three openings, taking the last of them.
The Frenchman stuttered badly when serving for the championship and lost one of his breaks as Auger-Aliassime belatedly rallied, but the victory was eventually sealed.
The Frenchman, winner of the Open sud de France last week, made it seven wins in a row by overcoming Evans in one hour and 52 minutes.
Next up in the last four is Filip Krajinovic, who upset the form book to overcome Andrey Rublev 7-6 (7-2) 6-4.
Felix Auger-Aliassime defeated Aljaz Bedene and will face Pablo Carreno Busta, who needed three sets to see off Jannik Sinner, in the other semi-final.
The highest-ranked Brazilian in the field made a winning start at South America's only ATP 500 event, but he had to work for it, emerging victorious after an 88-minute third set.
A raucous crowd cheered on every point down the stretch, and after saving four break point opportunities to force a tiebreaker, he jumped ahead to a 5-1 advantage and served it out.
He will face the winner between second seed Cameron Norrie and rising Argentine talent Juan Manuel Cerundolo in the next round.
Meanwhile, the top seed in action on Monday – third seed Lorenzo Musetti – continued his recent rough stretch of form with a disappointing 6-4 6-1 defeat at the hands of Chile's Nicolas Jarry.
Musetti, already ranked 18th in the world at 20 years old, has now lost four of his past five matches, while Jarry has won eight out of 10.
Jarry will play Spain's Pedro Martinez in the second round after he spoiled a potential all-Chilean matchup, eliminating Cristian Garin 7-6 (7-0) 6-4.
The only other Brazilian in action, Joao Fonseca, had no luck against Slovakia's Alex Molcan as he went down 6-0 6-3, while Bolivia's Hugo Dellien was similarly dominant in his 6-0 6-2 trouncing of Portugal's Joao Sousa.
After taking a set off world number two Carlos Alcaraz at last week's Argentina Open, Laslo Djere advanced into the second round as Facundo Bagnis retired in the second set while trailing 6-2 3-2.
The top seed had ended a dismal losing streak with victory over Richard Gasquet in the first round and looked to be on course to advance again when he took the first set against Opelka.
But the 6ft 11in American responded to prevail 2-6 7-5 6-4 after successfully defending four Medvedev break points in the third set.
The world number six, who reached the US Open semi-finals before embarking on this desperate run, is the biggest scalp of Opelka's career.
"It is always a tough match, playing one of the best players in the world in general but especially at home," the victor said. "[It is] a great win for me.
"It was ugly for the first set and a half. I felt like I barely won any points on his serve, but part of that is just because of my opponent. Daniil is an absolute nightmare to play."
Medvedev smashed his racket into the court at the end of another frustrating contest.
Russia's other big names will at least fly the flag, as Andrey Rublev and Karen Khachanov progressed.
Rublev's comeback win over Ugo Humbert was a big one for the third seed, who is closing on a place in the ATP Finals. Canada's Denis Shapovalov is also in the running and remains in the hunt for the title this week.
Alexander Zverev eased through at the Cologne Indoors, beating Fernando Verdasco in straight sets, but Marin Cilic exited at the hands of Alejandro Davidovich Fokina.
Cilic led by a set and a break, then had two opportunities to break back in front at 5-5 in the second, before losing 3-6 7-6 (7-3) 6-2.
At the Sardegna Open, Casper Ruud was the victim of the day's biggest upset.
The third seed's prior five defeats since the ATP Tour returned in August had come against top-20 players, but he went down 6-2 6-1 to 101st-ranked Yannick Hanfmann.
Murray, a five-time champion at Queen's, was beaten 6-3 6-3 by Italian Berrettini as the three-time grand slam champion struggled a day on from being given a Wimbledon wildcard.
The former world number one beat Benoit Paire in his first ATP Tour singles match since March on Tuesday, but the 34-year-old revealed he is still being troubled by a groin injury after his loss to Berrettini and knows he must raise his game.
Murray said: "I actually felt my movement was actually quite good for both of the matches. My tennis today was not very good. That's the thing that I'll need to improve the most.
"Then there is still a slight niggle in the groin, so [I have] to try to get rid of that discomfort between now and Wimbledon. I need to be playing points, basically. I played two sets in preparation for this event.
"I do feel like I genuinely have been hitting the ball well in practice, but then like today when you're under a bit more pressure and stuff and you're having to make very split-second decisions when you're on the court, if the guy is serving 140 miles an hour, like, it's difficult to prepare for that."
Dan Evans made history earlier in the day, getting the better of Adrian Mannarino 6-4 7-6 (9-7).
With Jack Draper and Cameron Norrie having already progressed, Evans' win ensured there will be three Britons in the singles quarter-finals for the first time in the Open Era.
Feliciano Lopez will not retain his title in London after the Spaniard went down 6-2 6-3 to second seed Denis Shapovalov. Spanish veteran Lopez won in 2019, with last year's tournament cancelled due to the pandemic.
There will be no glory on home soil in Halle for German Zverev, who was taken out 7-6 (7-4) 3-6 6-3 by unseeded Frenchman Humbert.
Humbert has now beaten a top-10 player on every surface, with Zverev serving 20 aces but bowing out after his 22-year-old opponent claimed the only break of the final set.
Sebastian Korda battled past Kei Nishikori 2-6 6-3 7-5 in Halle, while Lloyd Harris also moved into the last eight at Lukas Lacko's expense.
Murray, who triumphed at this tournament in 2009, battled past Alexander Bublik in his opening match but struggled to replicate that form against Auger-Aliassime on Thursday.
The Scot was never in control against the world number nine, who will face Murray's fellow Briton Cameron Norrie in the quarter-final, as he was downed 6-3 6-4 by the third seed.
"From the start of the match I was ready and focused and I think that is why I was able to produce a high level from the first point," Auger-Aliassime said on court after his victory.
"He made me bring out my best tennis and I am really happy with the way I played and that I was able to stay ahead. [To] win in straight sets is a great relief."
Top seed Tsitsipas, who was a beaten semi-finalist in this event last year, made light work of Ilya Ivashka as he raced to a 6-4 6-1 triumph in just one hour and 11 minutes to tee up a last-eight meeting with Alex de Minaur.
Reigning champion Rublev cruised past Soonwoo Kwon in similar fashion with a 6-3 6-3 win to secure his seventh straight victory at the ATP 500 tournament.
Meanwhile, qualifier Jiri Lehecka recovered from a first-set scare against Botic van de Zandschulp to succeed 1-6 6-4 6-4, with Lorenzo Musetti awaiting the Czech in the next round.
Murray had hip surgery in 2019 and had not won a grass-court game since 2018, with last year's season having been cancelled due to the coronavirus pandemic.
Having struggled with a groin injury, the 34-year-old Scot last played in March, yet showed flashes of his old self in his 6-3 6-2 victory over Benoit Paire, having taking up a wildcard into the pre-Wimbledon tournament.
It was an emotional moment for Murray, who said: "Look, I love playing tennis."
The five-time champion was fighting back the tears as he continued: "Obviously, competing is why you put in all the hard work.
"The last few years, I've not got to do that as much as I would have liked so, yeah it's just great that I'm out here and able to compete again.
"The body is old, but I did quite well today in terms of my movement.
"It's my first match on grass in three years and I've only played three or four practice sets in the build-up to this, so I didn't know exactly how I was going to play or feel – but I think for a first match it was good."
Murray will face top seed and world number nine Matteo Berrettini, who defeated Stefano Travaglia 7-6 (7-5) 7-6 (7-4).
British number one Dan Evans beat Alexei Popyrin, while fourth seed Alex de Minaur also progressed to round two, having come from behind against Laslo Djere. Second seed Denis Shapovalov overcame Aleksandar Vukic.
Tuesday's results mean, for the first time since 2005, four British players have won at Queen's, with Cameron Norrie and Jack Draper having gone through on Monday.
Meanwhile, after losing to Stefanos Tsitsipas in the French Open quarter-finals, world number two Daniil Medvedev crashed out of the Halle Open in the first round.
Jan-Lennard Struff was his conqueror, claiming a 7-6 (8-6) 6-3 triumph, which the German labelled as "the biggest win of my career."
There was better luck for third seed Alexander Zverev, though he did need three sets to see off Dominik Koepfer 6-4 3-6 6-3, just four days after facing Tsitsipas in the Roland Garros semi-finals.
Ugo Humbert awaits Zverev, while Felix Auger-Aliassime beat Hubert Hurkacz to tee up a tie with Roger Federer. World number seven Andrey Rublev got the better of Karen Khachanov.
Former world number one Murray secured an impressive 7-6 (8-6) 6-4 victory over Alexander Bublik, who entered the tournament on the back of the biggest win of his career over Alexander Zverev in the Montpellier final last week.
Murray stopped the Kazakh serving out the opening set with a crucial break and appeared in fine form as he closed out the win.
"There were some tough moments in the first set for both of us. I just managed to come through at the end of it. Some great returns off some big second serves from him at the end and I did a good job," said Murray.
"It’s not easy playing against someone like that, huge serves, a lot of drop shots and you’ve got to keep your focus and I did that well."
Up next for Murray is Australian Open quarter-finalist and third seed Auger-Aliassime, who came from a set down to beat qualifier Egor Gerasimov 3-6 6-2 6-2.
"[Auger-Aliassime] started the year pretty well and is one of the best young players just now," said Murray. "I'll need to be on my game if I want to beat him, but it's a great test for me and we'll see what happens out there."
Musetti advanced to the quarter-finals after a 6-3 5-7 6-4 triumph over Hurkacz, dropping just one point on his first serve in the decisive set.
Cameron Norrie defeated Karen Khachanov 6-4 7-6 (7-5) to reach the last eight, while Alex De Minaur was also a 7-6 (8-6) 1-6 6-4 victor against Mackenzie McDonald in the second round.
Murray reached the final of the Qatar Open, which he lost 6-4 6-4 to Daniil Medvedev on Saturday, and had to play three sets in every match during his run to the showpiece.
The world number 52 impressed in Doha, including beating Alexander Zverev and saving five match points against Jiri Lehecka in his semi-final.
However, the toll on the 35-year-old seems to have led to his decision not to participate in Dubai, with the tournament beginning on Monday.
A statement from the tournament read: "We regret to inform you that Andy Murray is unable to participate in this year's tournament.
"Andy has been dealing with a recurring hip injury that has unfortunately forced him out of Dubai. We wish Andy a speedy recovery and hope to see him back on the court in Dubai soon."
Murray's win over Lehecka in Qatar meant he moved level with Jimmy Connors in fifth on the list for most ATP hard-court wins in the Open Era (489).
Top seed Alcaraz ensured he would become the youngest player in the top five of the ATP rankings since Rafael Nadal in 2005 with his semi-final victory over Alex Molcan.
But the 19-year-old paid the price for an error-strewn display on Sunday, as Musetti, 20, took the crown 6-4 6-7 (6-8) 6-4.
Alcaraz was guilty of a slow start on the clay, with four wild unforced errors helping Musetti go a break up after the very first game. Although the Spaniard instantly hit back, his opponent gobbled up his next break point to take a 4-3 lead en route to winning the set.
Musetti then took charge early on in the second to go 2-0 ahead, but Alcaraz showed admirable resolve to see off a couple of match points and level the set at 5-5, before remarkably tying the contest in a tie-break that saw three more championship points squandered.
The deciding set was evenly contested almost throughout, until Musetti broke serve to make it 6-4 and take the match on his sixth championship point as Alcaraz hit a backhand long.
On a momentous day for the Italian, his jubilation was plain to see as he spoke afterwards.
"I have no words because it was a rollercoaster until the end," Musetti said on court. "I had so many match points. Carlos was so good on the match points, [I had] so many chances.
"But I think the key of the match was to keep calm and [have] all the patience [with] myself because it was really not easy.
"Carlos was putting so much effort in the match points when he was down, so it was not easy to find the energy to come back.
"But I cannot describe what I am feeling right now. I think I am still dreaming."
On the subject of the five match points he surrendered, Musetti added: "Of course I was really upset, but I tried to not show my opponent my reaction.
"I tried to forgive [myself for] all the match points and all the points [when] I couldn't do it. I think that was the most [important] thing, even for me, because I didn't expect the win after all this rollercoaster, so I'm super happy to be here and to be the champion."
Musetti and Alcaraz could end up meeting again in the coming week in Umag, where the latter is the defending champion and top seed.
