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The Croatian, whose last semifinal appearance at a major was at the 2018 Australian Open when he reached the final, encountered stiff resistance from Rublev but his 33 aces made the difference.
The 2014 US Open champion, seeded 20th, dominated proceedings from the start and finished off the contest in an hour and 45 minutes to reach the last eight stage on the Parisian clay for the third time in his career.
The US Open champion played near-flawless service games throughout the match.
Clay courts have not been Medvedev's strong suit and he was 0-4 at Roland Garros before last year's tournament but turned around his dismal record by reaching the quarterfinals of the 2021 edition of the Grand Slam.
The The All England Lawn Tennis Club also added that banning Russian and Belarusian players from this year's Wimbledon championships was the only viable option under the guidance provided by the British government.
Russian players will not be allowed to compete at Wimbledon this year due to Moscow's invasion of Ukraine, according to a report in sports industry news site Sportico on Tuesday.
Finland, which shares a 1,300-km (810-mile) border with Russia, and Sweden are considering joining the NATO alliance. Finland will decide in the next few weeks, Prime Minister Sanna Marin said on Wednesday.
Wimbledon can take stricter measures as the tournament "possesses a different status", the report added.
US President Joe Biden called for a war crimes trial against Russia's President Vladimir Putin and the United States will ask the UN General Assembly to suspend Russia from the Human Rights Council.
Mariupol has suffered the worst humanitarian catastrophe of the war, with hundreds of thousands of civilians trapped in basements with no food, water or power for weeks.