The world number two has 86 singles titles, including 20 majors, to his name, yet the season-ending showdown is not counted among his honours, and it was Medvedev who progressed to a final with last year's runner-up Dominic Thiem thanks to a 3-6 7-6 (7-4) 6-3 success.
A year ago during round robin play at the ATP Finals in London Medvedev blew a 5-1 lead and failed to convert a match point in the third set against Nadal before falling 6-7 (3) 6-3 6-7 (4), but on Saturday the Russian made the bold chess moves when they were necessary and he pushed past Nadal even after the Spaniard served for the match at 5-4 in the second set.
Medvedev led Nadal 5-1 in the third set during a round-robin clash a year ago only to lose, while he was also beaten in five sets by the Spaniard in the 2019 US Open final.
Djokovic has beaten Thiem in seven of their 11 meetings, but the Austrian came out on top in London past year and in the French Open semi-finals before Djokovic gained revenge in a five-set Australian Open final.
Thiem beat Medvedev in the semi-finals of the US Open in September before going on to win his first Grand Slam title.
Rafael Nadal will take on Daniil Medvedev in the other semifinal match.
"It was for sure a mental battle".
"At 5-4 in the second set I made a decision to change some small things and start going for things a little more. I thought after winning the title in NY I would be more calm, but that was a mistake I guess". I mean, the relationship between me and the players won't change. "He just took it away from me". "I'm incredibly happy to be through".
"I think it's super for tennis", he said.
"Anyway now we're going to have again a first-time victor, no matter what happens in the second semi-final".
But he was unable to make his chances count and a drop in his level allowed the Spaniard to break to love to lead 5-3 before he served out for the set. We are starting to make our mark. Dominic won his first Slam [and he is] playing unbelievable tennis right now. The Spaniard, who clinched a record 13th Roland Garros title in October, said the reverse was a combination of some good tennis by his opponent and poor play by him. I felt like I had the chances to win before (in) some games, a set maybe, but it didn't work, so I had to change and it worked really well.
It seemed like he had exhausted the wily Russian's box of tricks when he served for the match at 5-4 in the second set but Medvedev, 10 years his junior at 24, stormed back to win 3-6 7-6 (4) 6-3. Hopefully I can play good like this.
By the start of the third set, Medvedev had struck twice the number of total winners and made just three more unforced errors than Nadal, suggesting that Medvedev's aggressive, courageous play was additionally accurate.
Thiem leads his ATP Head-to-Head series against Medvedev 3-1.
"I don't know what happened. I'm feeling confident. I think Rafa is also".