Federer, a seven-time champion, was ousted from one of his favourite tournaments in barely over an hour, falling in straight sets to a 21-year-old Andrey Rublev he had never faced.
The 33-year-old Spaniard becomes the first player, man or woman, to win the same Slam 12 times after seeing off a brave challenge from a weary Thiem of Austria in a repeat of the 2018 final.
Ashleigh Barty ended Australia's 46-year wait for a French Open singles title by thrashing nervous Czech teenager Marketa Vondrousova in a one-sided women's final.
Tsitsipas had never won a set in his previous three meetings against claycourt specialist and 11-times French Open champion Nadal, but the Greek drew first blood by saving a break point to hold in the 10th game and take the first set.
Rafael Nadal showed no signs of rust as he raced into a 5-0 lead against fellow Spaniard Roberto Bautista Agut in the first set on Court Rainier III, defending his Monte Carlo Masters title with 6-1, 6-1.
Stefano Tsitsipas downed Wimbldon finalist Kevin Anderson in three sets to set up a meeting on his 20th birthday with Rafael Nadal,
As the Spaniard overcame Marin Cilic it was the Greek teen Stefanos Tsitsipas who was the talking point after he defeated defending champion Alexander Zverev in three sets.
Nadal earns a record-extending 11th championship at Roland Garros. The victory allows the 32-year-old Spaniard to hold onto the No. 1 ranking.
Rafael Nadal is now just the second man to reach 11 finals at the same Slam, equalling Roger Federer’s mark at Wimbledon.
Alexander Zverev overcame Russian in five sets while Austrian Dominic Thiem downed Japan's Kei Nishikori in four sets.
Austrian Dominic Thiem beat the top-ranked Rafael Nadal 7-5, 6-3 in the Madrid Open quarterfinals on Friday, ending the defending champion's run of 21 straight wins on clay courts.
Antalya Open is the final destination for top tennis players this year before Wimbledon next week.
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