World no. 3 in men’s singles, Nadal beat Argentine opponent Diego Schwartzman 3-1 with sets of 6-3, 4-6, 6-4, 6-0 in the quarterfinal match in Paris.
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The Spaniard recovered from a potentially dangerous fall after tripping over a raised line to take the latest installment of the most-played rivalry in modern men’s tennis.
The final in Rome is the 57th time they play against each other in history; their last encounter was at the 2020 French Open final, where the Spaniard won in straight sets.
Rival Novak Djokovic had already sealed his progress earlier in the day, beating Alejandro Davidovich Fokina in dominant fashion, but Nadal found life hard against Denis Shapovalov.
Nadal, the 20-time Grand Slam champion from Spain, is a two-time Olympic gold medallist, having won the singles event in Beijing and the doubles eight years later at the 2016 Rio Olympics.
Zverev is looking for his first Masters title since he got the better of Thiem in the final in the Spanish capital three years ago.
World number two Nadal claimed his fourth Laureus award as he was recognised for his 13th French Open and record-equalling 20th major.
Nadal, who returned to number two in the world last week after his thrilling win over Stefanos Tsitsipas in the Barcelona final, strolled past his 18-year-old opponent in the Spanish capital.
Nadal trailed 4-2 in the opener but recovered, breaking twice to take it.
The 11-time tournament champion looked ready to roll to a quick victory after dominating the first set, but Nishikori responded with some fine net play to level it at 1-1.
The Greek 22-year-old world No. 5 took one hour and 11 minutes to beat the Russian, ranked eighth, for the best victory in his career, after his triumph in the year-end Masters in 2019.
Djokovic produced a clinical 6-4 6-2 win over up-and-coming Jannik Sinner on Wednesday before Nadal, the 11-time champion at the Country Club, thrashed Federico Delbonis 6-1 6-2.
The World no. 7 is the highest-ranked player who has withdrawn from Miami so far, joining Roger Federer, Rafael Nadal, Dominic Thiem and Novak Djokovic on the list of the most notable missing players.
The Spanish superstar was unable to compete at the ATP Cup earlier this month due to back stiffness, but recovered to reach the Australian Open quarter-finals (l. to Tsitsipas).
His latest triumph in Melbourne has brought the 33-year-old world number one Djokovic to within two of the record mark of 20 major wins shared by Roger Federer and Rafael Nadal.
The world number one, who has won the title on each of the eight previous occasions he has reached the semi-finals in Melbourne, claimed his first straight-sets win since the first round, beating the world number 114 6-3 6-4 6-2.
Second seed Nadal was on course for a comfortable victory before Tsitsipas turned the match around to prevail 3-6, 2-6, 7-6 (7/4), 6-4, 7-5 in a seismic upset.
The second seed came into the tournament with serious concerns over a back problem but revealed after beating Britain’s Cameron Norrie in the third round that it had finally started to improve.
The council, as voted by ATP player members, also saw the re-election of Canadian Felix Auger-Aliassime, Australian John Millman, South African Kevin Anderson, Briton Andy Murray and Brazilian Bruno Soares.
In a season that was defined by the coronavirus pandemic, Nadal has sent a message in support of the people who have lost loved ones and paid tribute to all the health workers.