Defending men's champion and 24-time Grand Slam champion Novak Djokovic will face French veteran Pierre Hugues-Herbert in his opener.
Nadal, who has won Roland Garros on 14 occasions, is unseeded after injury saw his ranking plummet to 276.
He and Zverev met in the semi-finals in 2022 when the German was forced to retire after suffering a serious ankle injury.
Nadal, the winner of 22 Grand Slam titles, will turn 38 next week and this season will be his last on tour.
He holds a 7-3 winning head-to-head record against Germany's Zverev with five of those victories coming on clay.
Zverev, 27, arrives in Paris on the back of lifting the Rome Open title last weekend.
"I'm going to play the French Open thinking that I can give my all, 100 per cent," said Nadal after a second round exit in Rome last week.
As well as 14 titles in Paris, Nadal can boast a record of 112 wins and just three losses, two of which came against Djokovic who will be chasing a fourth French Open title.
Djokovic turned 37 on Wednesday and marked the occasion by winning the 1,100th match of his career in Geneva.
The Serb has yet to win a title in 2024 with runs to the semi-finals at the Australian Open and Monte Carlo Masters his best performances.
Following Thursday's draw, Djokovic is seeded to face Zverev in the semi-finals.
World number two Jannik Sinner, who took Djokovic's Australian Open title in January, faces Christopher Eubanks of the United States.
Third-seeded Wimbledon champion Carlos Alcaraz, a semi-finalist in Paris in 2023, plays a qualifier.
Sinner and Alcaraz are seeded to meet in the semi-finals but both men have been suffering from injuries which forced them to skip the Rome event.
Murray v Wawrinka
Andy Murray, the 2016 runner-up, is also competing at the tournament for the final time.
The 37-year-old tackles 2015 champion Stan Wawrinka, 39, in a battle of grizzled Grand Slam veterans.
The pair have met 22 times in a two-decade rivalry with Murray boasting a 13-9 edge.
Three of those clashes have come at Roland Garros with Murray winning in the semi-finals in 2016 while the Swiss came out on top in the last-four in 2017 and first round in 2020.
In the women's draw, top seed and world number one Swiatek will take on a qualifier with Osaka facing Lucia Bronzetti of Italy in their openers before a potential second round clash.
Swiatek is bidding to win a fifth major and fourth French Open title.
"It feels like home here," said Swiatek who arrives at the tournament with clay-court titles in Madrid and Rome under her belt.
Former world number one Osaka, now ranked 134, has never got past the third round in Paris. Bronzetti, the world number 48, has yet to win a main draw in two visits.
Osaka, 26, has endured a bittersweet relationship with the French Open.
In 2021, she was fined for opting out of mandatory media commitments before withdrawing from the competition after just one match insisting she was protecting her mental health.
Osaka missed the 2023 edition due to being pregnant before giving birth to a baby girl in July.
Swiatek, meanwhile, is bidding to become the first player to lift three successive women's titles in Paris since Justine Henin in 2007.
World number two Aryna Sabalenka starts against 101-ranked Erika Andreeva of Russia.
Third seed and US Open champion Coco Gauff faces a qualifier in the first round and is seeded to face Swiatek in the semi-finals.
Double Australian Open champion Sabalenka is seeded to take on former Wimbledon winner Elena Rybakina in the last four.
