World number 14 Goffin had lost his previous three matches heading to Monaco, but the Belgian delivered a sharp performance on Sunday, winning 6-4 3-6 6-0.
Open Sud de France champion Goffin did not start well, and had to come from 3-0 down in the first set, but Cilic made 52 unforced errors to help his opponent progress.
"It’s a good win. [This is my] first tournament on clay [in 2021]. Starting with a victory is good," said 2017 Monte Carlo semi-finalist Goffin, quoted on the ATP website.
"I did what I needed to do to win that match. I was playing better and better. In the first and second set, I had problems with the returns. In the third set, I was more consistent. It was a good match."
Goffin will face Marco Cecchinato or Dominik Koepfer in the second round, where he has been joined by Australian Jordan Thompson.
Thompson, the world number 62, needed three hours and two tie-breaks to beat Paire 6-4 6-7 (3-7) 7-6 (7-5), as the Frenchman's dismal string of results in 2021 continued.
Paire has now won just one of 10 matches this calendar year, while Thompson registered a fifth win of the season.
After Roberto Bautista Agut beat Steve Darcis' replacement Kimmer Coppejans 6-1 6-4 in the first singles match, a win for Nadal would have sent Spain through to the semi-finals in Sydney.
However, Goffin got the better of the 19-time major winner for only the second time in his career with a fine attacking display.
The Belgian was unable to consolidate his first break of the opening set but, after staving off a trio of break points in game eight, he did not fail at the second attempt.
Goffin continued that momentum with a break early in the second, before Nadal fought back to force a tie-break.
However, the world number one double faulted at 5-2 down to give Goffin four match points and he only needed two attempts to convert and take the tie the distance.
"I felt my tennis the other match against Grigor [Dimitrov]…the confidence came back and I was ready for the fight tonight," Goffin said on court.
"From the first point until the end it was not easy, I was up a set and a break and I had to hold my nerves until the end. I played a very good tie-break, some tough games towards the end of the second to hold my serve but at the end I'm so happy for Belgium to have a decisive doubles.
"I knew Rafa had to take the ball a little bit early, maybe to take some more risks because I was in the court trying to dictate all the time and he had to find a solution. He finds a solution most of the time so I had to stick to my line and continue to move forward."
Goffin, who won the event in 2014, fell to a 6-3 6-3 defeat to three-time champion Gilles Simon, who is set to retire at the end of the 2022 campaign.
Simon needed 93 minutes to wrap up his victory over the four-time grand slam quarter-finalist, teeing up a round-of-16 meeting with Italy's Lorenzo Sonego.
"We've known each other for a very long time and I’m always happy to play against [Goffin] one more time before the end," Simon said after the win.
"It was really perfect from the start until the end and that's how I won this one."
Elsewhere, Basilashvili was a set down in his meeting with Bergs when the Belgian qualifier was forced to retire through injury, allowing the fifth seed to progress to a meeting with Arthur Rinderknech.
Rinderknech downed Spain's Jaume Munar in three sets to reach the next round, while Emil Ruusuvuori comfortably saw off Jiri Lehecka 6-4 6-4.
World number 10 Goffin has started the season in impressive form and remains on course for a first ATP Tour title since Tokyo in 2017.
The second seed bested Bublik's varied strokeplay over the course of one hour and 47 minutes, with the 22-year-old even serving underarm in a bid to deceive Goffin as a gripping second-set tie break slipped away.
Goffin will face Pierre-Hugues Herbert in the quarter-finals after the home favourite claimed an impressive 7-6 (7-2) 7-5 triumph against Felix Auger-Aliassime.
Herbert was a finalist in Montpellier last year, while countryman Richard Gasquet remained in contention for his fourth win at the event by beating Feliciano Lopez 6-7 (1-7) 6-4 6-2.
Vasek Pospisil, a winner in the all-Canadian clash with Denis Shapovalov on Wednesday, is up next for Gasquet, who retained his place in a draw stacked with French hopes.
Gael Monfils came from a set down to beat compatriot Adrian Mannarino 4-6 6-1 6-4, joining Gregoire Barrere – a shock winner over Grigor Dimitrov a day ago - in the last eight.
Filip Krajinovic will be Barrere's next opponent after demolishing qualifier Mikael Ymer 6-1 6-1, with Norbert Gombos also seeing off Emil Ruusuvuori in straight sets.
At the Pune Open, top seed Benoit Paire was dumped out in straight sets by Roberto Marcora – the Italian qualifier prevailing 6-4 6-4.
Elsewhere, seeds Ricardas Berankis, Kwon Soon-woo, Yuichi Sugita, James Duckworth and Egor Gerasimov emerged unscathed to reach the quarter-finals.
The former world number seven is in the hunt for a first title of the season, and defeated Damir Dzumhur 6-2 7-6 (7-3) in his first match on Wednesday.
That victory teed up a last-16 tie with Andujar, who defeated second seed Dan Evans in his first-round match.
The 36-year-old Spaniard is something of a specialist in Marrakech, having won this tournament three times, in 2011, 2012 and 2018.
Young Italian prospect Lorenzo Musetti overcame Andujar's compatriot Carlos Taberner 6-1 6-7 (3-7) 6-3 to become the first player to reach the quarter-finals.
Musetti, who reached the last 16 at last year's French Open and featured at the ATP Next Gen Finals, has had a tough start to 2022, only reaching one other quarter-final so far.
Serbian eighth seed Laslo Djere followed Musetti into the last eight by beating Malek Jaziri 6-4 6-2.
Qualifier Mirza Basic sprung a surprise to overcome Kamil Majchrzak 4-6 6-4 6-1, while Vit Kopriva defeated Bernabe Zapata Miralles in straight sets.
World number 172 Pavel Kotov claimed the scalp of a top-100 player, bouncing back from a first-set bagel to beat Tallon Griekspoor 0-6 6-2 6-2.
Fourth seed Hurkacz, who was beaten in the second round in Melbourne by Adrian Mannarino, saw off wildcard Tsonga 6-4 7-6 (9-7) in one hour and 32 minutes.
"Jo is an amazing player and competitor," Hurkacz said of the former world number five.
"He brought a really high level and it was a really tough match for me and he is definitely on the way back.
"Jo has achieved so much in his career and playing against him you can see why with his shots and his serve. I appreciated playing him and I am happy with the win today."
World number 11 Hurkacz will face either Lorenzo Musetti or Mikael Ymer in the second round.
Sixth seed Cameron Norrie overcame Ugo Humbert 6-2 6-4, while eighth seed Nikoloz Basilashvili was dumped out by American Mackenzie McDonald 6-3 6-2.
McDonald will face Alex de Minaur in the next round after the Australian swatted aside David Goffin 6-0 6-3.
"I think I played really well," De Minaur said. "I played exactly how I wanted to. My coach and I set up a plan about how we wanted to play this match and I managed to execute it.
"It is a very good feeling. Mentally I thought I was very solid and positive and that is one of the main aspects I am trying to focus on this year."
Kyrgios suffered a disappointing semi-final defeat to Andy Murray in Stuttgart last week, but looked greatly improved against Tsitsipas as he recovered from a set down to win 5-7 6-2 6-4.
It was the second serve of both men where Kyrgios shone, winning 76 per cent (28 of 37) of points on his second serve, and 58 per cent (23 of 40) on his opponent's.
"Stef is one of the best players in the world at the moment and he's going to have some amazing results and I'm sure many, many grand slams," Kyrgios said following his win.
"I don't know if I can say the same for me, but I'm happy to still be able to produce this level with the tournaments I play. It is a testament to how hard I do work when I'm not playing."
He will face Pablo Carreno Busta in the quarter-finals after the Spanish sixth seed beat Sebastian Korda 6-4 0-6 6-3.
Elsewhere, Hubert Hurkacz will face Felix Auger-Aliassime in the last eight after defeating Ugo Humbert 7-6 (7-5) 6-3, while the Canadian also won in straight sets against Mackenzie McDonald 7-6 (9-7) 6-1.
The one remaining first round match saw number one seed Daniil Medvedev beat David Goffin 6-3 6-2 to set up a second round clash with Ilya Ivashka.
At the Queen's Club Championships, sixth seed Denis Shapovalov was eliminated by Tommy Paul 6-4 2-6 6-4, with the American now scheduled to face Stanislas Wawrinka in the second round.
It means that six of the eight seeds in west London were knocked out in the first round, with Matteo Berrettini and Marin Cilic the only remaining seeds. The latter sealed his place in the quarter-finals on Wednesday with a 7-6 (8-6) 7-5 win over Alexander Bublik.
Cilic will play Finland's Emil Ruusuvuori in the last eight after he beat home favourite Jack Draper 6-2 7-6 (7-2).
The best contest of the day came between Alejandro Davidovich Fokina and Alex de Minaur, with the former coming from behind to win 4-6 6-4 7-5 to set up a quarter-final with Botic van de Zandschulp, who beat Grigor Dimitrov 7-6 (7-5) 6-3.
Kyrgios beat Jan-Lennard Struff 6-4 7-6 (7-4) in Brisbane, sending down 20 aces after his pledge to give 200 Australian dollars to the bushfires effort for each service winner he hits in January.
Alex de Minaur – Kyrgios' team-mate at the event, who impressively came from a set down to defeat an ill-tempered Alex Zverev 4-6 7-6 (7-3) 6-2 – followed suit after Kyrgios tweeted his intention to help, while stars from other sports have also joined in.
Brisbane Heat captain Chris Lynn struck three sixes as he top-scored in his team's win over Hobart Hurricanes in the Big Bash League on Friday, with each maximum worth $250 to the recovery effort.
"I don't really care about the praise too much. I just think we've got the ability and platform to do something like that," Kyrgios told Amazon Prime when asked about the movement he inadvertently started.
"My home town is Canberra and we've got the most toxic air in the world at the moment, so it is pretty sad. It's tough."
Having appeared choked up at that point, Kyrgios added: "I just chucked up a tweet and everyone got behind it. It is bigger than tennis.
"It's going to all the families, firefighters, animals, everyone who is losing homes, losing families. It's a real thing.
Australia completed a 3-0 Group F win after Chris Guccione and John Peers beat German doubles pair Kevin Krawietz and Andreas Mies 6-3 6-4.
In the section's other match, Canada were similarly emphatic against Greece, with Denis Shapovalov winning a pair of tie-breaks to best Stefanos Tsitsipas after Felix Auger-Aliassime demolished Michail Pervolarakis 6-1 6-3.
Auger-Aliassime and Shapovalov then combined to win the doubles rubber against the same opponents, prevailing 6-2 6-3.
Great Britain and the United States both allowed leads to slip against Bulgaria and Norway respectively.
In Group C, Cameron Norrie beat world number 423 Dimitar Kuzmanov in three sets and Dan Evans made a fast start against Grigor Dimitrov to go a set up.
But Dimitrov prevailed 2-6 6-4 6-1 and he and Alexandar Lazarov triumphed after three tie-breaks against Jamie Murray and Joe Salisbury in the small hours of the Sydney morning.
Taylor Fritz beat Viktor Durasovic 6-2 6-2 and John Isner had the USA in charge of the second singles rubber when he took the opening tie break versus Casper Ruud, only for two match points and a second breaker to go against him. He eventually lost, going down 7-5 in the deciding set.
Ruud and Durasovic then recovered from dropping the first set to beat Austin Krajicek and Rajeev Ram 10-5 in a match tie-break in Perth.
Steve Darcis and David Goffin inspired Belgium to a 3-0 Group C win over Moldova, while Daniil Medvedev's 1-6 6-1-6-3 victory against Fabio Fognini helped clinch a 3-0 victory for Russia against Italy in Group D.
The 18-year-old Sinner claimed the first top-10 scalp of his career when he beat David Goffin last week, but he did not have enough to hold on against Medvedev.
After world number five Medvedev was brushed aside in a 25-minute first set, the Russian claimed two vital breaks in the second set before taking the decider for a 1-6 6-1 6-2 victory.
Medvedev will next take on Gilles Simon - a Marseille champion in 2007 and 2015 - after the Frenchman overcame Aljaz Bedene 7-6 (8-6) 6-4 to reach the quarter-finals.
Meanwhile, Goffin suffered another upset, going down 6-4 7-6 (7-5) to Belarusian qualifier Egor Gerasimov.
Gerasimov's next opponent, Felix Auger-Aliassime, overcame Pierre-Hugues Herbert in a thrilling encounter, with the youngster coming out on top 6-0 6-7 (6-8) 7-6 (11-9).
Auger-Aliassime's Canadian compatriot Denis Shapovalov also made the last eight as 17 aces helped him defeat two-time finalist Marin Cilic 6-4 4-6 6-2, with the world number 15 to meet Alexander Bublik next.
Russuvuori bounced back after losing the first set, changing his tactics and overwhelming the German on Friday to set up a third round meeting with Mikael Ymer.
Ninth seed Grigor Dimitrov also bowed out, going down to Briton Cameron Norrie, while eighth seed David Goffin lost to James Duckworth.
World number two and top seed Daniil Medvedev eased past Lu Yen-hsun, while 11th seed Felix Auger-Aliassime, Karen Khachanov and John Isner all progressed.
TURNAROUND STUNS THIRD SEED
Zverev may have won last week's Mexican Open and the opening set 6-1 against Ruusuvuori but the tables turned quickly as the Finn produced one of the best displays of his career to date.
The 83rd ranked Finn moved regularly to the net and was aggressive in his approach, leaving Zverev rattled before winning 1-6 6-3 6-1 in a stunning momentum shift.
"I don't even know myself," Ruusuvuori said in his on-court interview when asked how he turned the match around.
"I wasn't feeling very comfortable in the first set and I was making a lot of unforced errors but slowly in the second I was starting to feel a bit better... Of course, it's one of the biggest wins in my career so it feels good."
He'll next face Ymer who knocked out 27th seed Nikoloz Basilashvili.
NINTH SEED BUNDLED OUT
Former world number three Dimitrov was ousted from the Miami Open on Friday, losing 7-5 7-5 to 56th ranked Norrie.
The Bulgarian took an early break and served for the first set at 5-3 but Norrie showed his mettle to break back twice to take the opener.
Norrie sent down 10 aces and was strong on serve throughout, claiming a significant win for his burgeoning career.
“It’s huge,” Norrie said. “He’s had a good start to the year. It was such a physical match at the start. He came out really fast and he set the tone at the beginning of the match. Massive one for me and I take a lot of confidence from it.”
Norrie's win sets up a third round meeting with American Taylor Fritz who beat Marcos Giron 6-2 6-2.
DANIIL DOMINATES, GOFFIN SHOCK
Australian Open runner-up Medvedev made light work of Lu, winning 6-2 6-2 to book a third round match with Australian 21-year-old Alexei Popyrin.
Medvedev won in less than an hour, hitting 24 winners and nine aces and making few errors in a clinical display.
Canadian 11th seed Aliassime proved too good for Pierre-Hugues Herbert 6-4 6-4, setting up a third round meeting with 18th seed John Isner who got past qualifier Mackenzie McDonald.
Seventh seed Roberto Bautista Agut progressed by virtue of a walkover against Lloyd Harris who had a wrist issue.
Eighth seed Goffin lost to world number 104 Duckworth 6-3 6-1 in a boilover.
The world number nine downed Slovakian Gombos 6-3 6-4 in Montpellier on Friday to stay in contention to win the tournament for a third time.
Filip Krajinovic stands in the way of Monfils and a place in the final after the seventh seed accounted for Gregoire Barrere 6-2 7-5.
Vasek Pospisil moved into the last four when Richard Gasquet retired at 6-1 1-0 down in his homeland due to an abdominal injury.
David Goffin will take on the Canadian after the second seed saw off Pierre-Hugues Herbert 6-4 7-6 (7-5).
James Duckworth reached his maiden ATP Tour semi-final with a 6-3 7-6 (7-4) defeat of qualifier Roberto Marcora at the Pune Open.
The 96-ranked Australia will come up against Egor Gerasimov, who came from a set down to beat Kwon Soon-woo 4-6 7-6 (7-1) 6-4.
Jiri Vesely and Ricardas Berankis will contest the other semi-final after getting past Ilya Ivashka and Yuichi Sugita respectively.
Seeking his third title at the event, world number nine Monfils triumphed 7-6 (7-4) 6-2 in 82 minutes against the Serbian.
Monfils saved all three break points against Krajinovic in an impressive victory that maintains France's perfect record of ensuring a home player reaches the final of the Montpellier tournament.
The 2010 and 2014 champion will meet Pospisil on Sunday after the Canadian defeated David Goffin in three sets.
Goffin served for the match in the decider but lost three decisive games in a row as Pospisil triumphed 6-3 1-6 7-5 in two hours and 21 minutes.
At the Pune Open, Australia's James Duckworth was beaten 7-6 (7-2) 6-4 by Egor Gerasimov in the semi-finals.
The Belarusian dropped only five points behind his first serve as he reached a maiden ATP Tour final, where he will face Jiri Vesely.
Vesely saved match points for the second round in a row, outlasting second seed Ricardas Berankis 6-7 (8-10) 7-6 (7-3) 7-6 (9-7) in a draining encounter to secure a first final in nearly five years.
Murray defeated the veteran Frenchman 6-4 6-4 on a rainy opening day in Cincinnati, capitalising on a strong service game to advance.
Murray had 14 aces to just two double faults and won 81 per cent of points on his first serve while saving four of the five break points he faced.
A two-time champion at the ATP 1000 event, he will face the winner of Tuesday's match between Alejandro Davidovich Fokina and ninth seed Hubert Hurkacz in the second round.
Two players who shared a birthday Monday also prevailed on their big day.
On the day he turned 20, 11th seed Jannik Sinner defeated Federico Delbonis 6-2 7-5, while 10th seed Diego Schwartzman had to work a bit harder on his 28th birthday to down Daneil Evans 6-2 4-6 6-3.
Elsewhere, 12th seed Felix Auger-Aliassime beat Marton Fucsovics 7-6 (7-0) 6-3, while 14th seed Alex de Minaur rallied to down Filip Krajinovic 0-6 6-4 6-4.
Fifteenth seed David Goffin fell 6-3 6-3 to Guido Pella in the only seeded upset of the day.
Other winners Monday included Karen Khachanov, Fabio Fognini, Lloyd Harris, Dominik Koepfer, Benoit Paire, Albert Ramos Vinolas and Mackenzie McDonald.
Among those set to play their opening matches Tuesday are third seed Alexander Zverev, who will face Harris, and sixth seed Denis Shapovalov, who plays Paire.
Spain took a 1-0 lead after Roberto Bautista Agut overcame Steve Darcis' replacement Kimmer Coppejans 6-1 6-4, but Nadal was unable to seal the deal against Goffin.
Goffin claimed just his second success over the 19-time major champion, producing an efficient attacking display to take a 6-4 7-6 (7-3) triumph.
Nadal returned to Ken Rosewall Arena for the decisive doubles match alongside Pablo Carreno Busta, but they failed to convert a set point before surrendering the opener to Sander Gille and Joran Vliegen.
Spain forced a match tie-break after a video review showed Vliegen struck the ball before it crossed the net and with momentum on their side, Nadal and Carreno Busta surged to victory.
Nadal found the corner with a tremendous forehand from the baseline for the first mini-break and a double fault from Gille gave them a second. A double fault from Vliegen sent Spain through to a showdown with Australia on Saturday.
"It was tough for us it was a big change from Perth to here with not much time to adapt and the conditions today were very heavy," said Nadal after the 6-7 (7-9) 7-5 10-7 success.
"They [Belgium] have been here for 10 days, for us it's the first day. Well done to them, a great level of tennis... We are super happy to be in the semi-finals."
Dusan Lajovic got Serbia, who received raucous backing from the crowd in Sydney, off to a great start by claiming a 6-4 6-2 victory over Felix Auger-Aliassime in an hour and 39 minutes.
Canada were consequently relying on Denis Shapovalov beating Djokovic in the second singles rubber to remain in the competition and hopes were high when he took the opening set of a heated encounter.
The world number two had to save three break points to avoid falling behind early in the second set, but his hold of serve kick-started a run that saw him reel off five straight games to force a decider.
Shapovalov received a code violation for unsportsmanlike conduct after reacting to boos from the crowd by swearing, though chair umpire Carlos Bernardes later told spectators who continued to jeer the Canadian to "go home".
The 20-year-old showed tremendous character to fight back and take the match to a final-set tie-break after Djokovic jogged to the stands to provide an unwell fan with water while serving for the victory.
Djokovic raced into a 6-1 lead in the tie-break and got the job done at the fourth attempt, completing a 4-6 6-1 7-6 (7-4) triumph.
Serbia finished off a 3-0 victory when Nikola Cacic and Viktor Troicki defeated Peter Polansky and Adil Shamasdin 6-3 6-2 in just 58 minutes. They face Russia in the semi-finals.
Nadal went into the meeting with a 73-5 record at the event but Russian Rublev was in inspired form to stun his Spanish opponent.
The 11-time champion looked set to complete a trademark comeback after taking a 74-minute second set, yet Rublev held firm in the decider to claim a memorable victory after two hours and 33 minutes on court.
"I cannot imagine being in the situation of Rafa, knowing that you are the best player on clay and you have that pressure every time," Rublev said, according to the ATP Tour website.
"I think for him it must be incredibly tough every time. I am in shock [with] the way he is playing under this pressure and that is why he is a legend."
Rublev will face Casper Ruud in Saturday's semi-final after he overcame defending champion Fabio Fognini 6-4 6-3.
Dan Evans followed up his superb victory over Novak Djokovic on Thursday with a slender win over David Goffin to reach his first Masters 1000 semi-final.
World number 33 Evans, who had come into the tournament having lost his previous 10 matches on clay, overcame Goffin 5-7 6-3 6-4 in two hours and 42 minutes.
"I am proud of how I came back today, especially with what happened in the first set," he said after the match.
"I felt my concentration wasn't great and I am really happy with coming through. Yesterday would not have been worth it with a bad performance today."
Evans will face Stefanos Tsitsipas, who progressed when opponent Alejandro Davidovich Fokina retired injured in their quarter-final.
Spaniard Davidovich Fokina did not return for the second set after earlier receiving treatment during the first, which Tsitsipas won 7-5.
Britain had last got their hands on the trophy in 1936, when Fred Perry and Bunny Austin helped defeat Australia.
When Murray completed a straight-sets win against David Goffin in Ghent to clinch it, he completed one of the most impressive feats of his career.
The Scot’s 6-3 7-5 6-3 triumph against the Belgian number one at the Flanders Expo was his 11th win in the competition that season.
Murray spearheaded the victory and claimed 11 of the 12 points which Britain needed for the title, eight in singles and three in doubles with brother Jamie. The only player not a member of the Murray family to contribute was James Ward.
Three other players have won 11 rubbers in a season since the current Davis Cup format was introduced in 1981, but Murray became the first to do so all in live rubbers and remain unbeaten.
On their way to victory, Britain defeated the United States 3-2 in Glasgow, France 3-1 in London and Australia 3-2 in the semi-finals in Glasgow before Murray sealed a 3-1 success against Belgium.
Murray said: “I probably haven’t been as emotional as that after a match that I’ve won.
“I’ve been pretty upset having lost matches before. But I’d say that’s probably the most emotional I’ve been after a win.
“It’s incredible that we managed to win this competition. I didn’t know that would ever be possible.”
Eighth seed Goffin, ranked at world number 52, prevailed 2-6 7-5 6-1 in Montpellier against the Frenchman.
It looked bleak for Goffin when Bonzi raced into a 3-0 lead in the second set, yet the Belgian reeled off three successive games to get himself back in the fight before snatching a crucial break to make it 6-5, and he did not look back from there.
"During the match I stayed positive even though I was one set and one break down," Goffin said.
"I tried to stay focussed, to stay as long as possible on the court to try to get some confidence, to work on certain things: to be more aggressive, [hit] a better quality of ball.
"At the end it was better and better, so I'm really happy the way I played at the end of the second and in the third."
Next up for Goffin is a tie with Spain's Alejandro Davidovich Fokina, or another Frenchman in the form of Adrian Mannarino, who lost to eventual Australian Open winner Rafael Nadal in Melbourne last month.
Monday's other match saw sixth seed Alexander Bublik defeat Tallon Griekspoor 7-6 (7-4) 7-6 (7-5).
Yuki Bhambri was the story at the Tata Open Maharashtra, as the Indian claimed a first tour-level match win in almost four years, beating Jozef Kovalik 6-7 (10-12) 6-2 7-5.
Bhambri, ranked at 863 in the world, had only played two singles matches on the ATP Tour since 2019 due to a knee injury and had last beat Mirza Basic in Miami in 2018.
"It is a privilege to play at home and it is an important win as well playing at my home tournament," he said. "Each match is tough at tour-level so I am just taking it one match at a time."
Radu Albot beat Federico Gaio in straight sets, while seventh seed Ricardas Berankis was shocked by Quentin Halys and Daniel Altmaier also progressed.
Second seed Schwartzman, ranked ninth in the world, needed just 81 minutes to seal a 6-3 6-2 victory, setting up a third-round meeting with Alejandro Davidovich Fokina.
It was a less happy outing for third seed Shapovalov in Germany, the Canadian succumbing to a 6-1 4-6 6-2 loss against Gilles Simon.
The result represented a measure of revenge for Simon after the Frenchman lost to world number 12 Shapovalov in the first round of the French Open.
"I am really happy with the way I played, with the focus I had over all of the match," Simon said in his on-court interview.
"I am really happy to beat him, because it is a very, very good win. I had a tough match with him at Roland Garros. I lost it unfortunately, so I am happy that I am the winner this time."
Jannik Sinner awaits for Simon after he defeated Pierre-Hugues Herbert, while Yoshihito Nishioka also made it through.
At the European Open in Antwerp, top seed and home favourite David Goffin suffered a stunning 6-3 7-5 defeat to American qualifier Marcos Giron.
Giron's surprise victory put him in the last eight of a ATP Tour event for the first time and he saved 10 of 13 break points he faced for a maiden victory over a top-20 opponent.
Milos Raonic was not to be denied a place in the quarter-finals, though, and a 7-5 7-6 (7-4) defeat of Cameron Norrie means he will now meet Grigor Dimitrov.
The Austrian downed the Argentinian in straight sets six days earlier in Gijon but found this a sterner test of his capabilities against the sixth seed.
Nevertheless, the former US Open winner shook off a second-set collapse and then responded to going a break down in the decider, winning four of the final five games to seal a quarter-final clash with favourite Hubert Hurkacz.
He was joined in the last-eight by two more unseeded players, as David Goffin and Sebastian Korda recorded straight-set upsets over third seed Diego Schwartzman and fourth-ranked Karen Khachanov respectively.
At the Stockholm Open, fifth seed Alex de Minaur made swift work of American J.J. Wolf, dispatching him in a 6-4 6-2 win to set up a quarter-final with Canada's Denis Shapovalov.
Defending champion Tommy Paul is out however, losing to Sweden's Mikael Ymer, who recorded a 6-2 6-3 victory that earns him a clash with top seed Stefanos Tsitsipas.
Slippery court conditions contributed to a backlog in fixtures at the Napoli Cup, meaning first-round matches were followed by second-round encounters on Thursday.
Nevertheless, second seed Matteo Berrettini made light work of Roberto Carballes Baena, winning 6-4 6-2.
Roberto Bautista Agut, seeded third, slipped to a 6-4 6-4 loss to Mackenzie McDonald, with the American joining Berrettini in the last eight.
Thiem was on the brink of being knocked out by the top seed in Antwerp, but fought back to win 3-6 7-6 (11-9) 7-6 (7-4).
The 2020 US Open champion fended off all three match points in a second-set tie-break to take a thrilling quarter-final the distance and then came out on top in another breaker to advance.
Thiem will do battle with Sebastian Korda for a place in the final after the American emphatically defeated eighth seed Yoshihito Nishioka 6-0 6-2.
Richard Gasquet moved into the last four at the expense of David Goffin and will face Felix Auger-Aliassime, who came from a set down to beat Dan Evans.
Matteo Berrettini remains in the hunt to win the Tennis Napoli Cup on home soil after a 6-2 6-3 quarter-final triumph over Taro Daniel.
Top seed Pablo Carreno Busta crashed out in Italy, losing 7-5 6-2 to Miomir Kecmanovic, who will face Lorenzo Musetti after he got the better of Daniel Elahi Galan. Mackenzie McDonald will come up against Berrettini after getting past Zhang Zhizhen.
Stefanos Tsitsipas sealed a Stockholm Open semi-final spot with a 7-5 6-3 win over Mikael Ymer and will take on Emil Ruusuvuori, who eliminated Frances Tiafoe.
Holger Rune and Alex de Minaur meet in the other last-four match in the Swedish capital following wins over Cameron Norrie and Denis Shapovalov respectively.
