Djokovic and Nadal lined up for potential second-round clash at Olympics
Nadal, a singles gold medallist at the 2008 Olympics, is playing in his final Games having also won doubles gold in Rio in 2016 while Djokovic was a bronze medallist in singles in 2008.
Djokovic, a 24-time major winner and top seed in Paris following the withdrawal of world number one Jannik Sinner, begins his campaign against Australia's Matthew Ebden.
Nadal, who has won 14 of his 22 Grand Slams on the clay of Roland Garros, faces Hungary's Marton Fucsovics in his opener.
French Open and Wimbledon champion Carlos Alcaraz, the second seed, faces 275th-ranked Hady Habib of Lebanon.
Two-time singles gold medallist Andy Murray, who will end his career at the Olympics after almost two decades on tour, will only play doubles.
The 37-year-old former world number one underwent surgery to remove a cyst on his back before Wimbledon, which also sidelined him from singles at the All England Club.
At the Olympics, he will play doubles with Dan Evans.
"I've taken the decision to withdraw from the singles to concentrate on the doubles with Dan," Murray said in a statement.
"Our practice has been great and we’re playing well together. Really looking forward to getting started and representing GB one more time."
See the full men's draw here.
Also making her last appearance will be Germany's Angelique Kerber, who announced Thursday that she will retire once the Games end.
The 36-year-old, who won three Grand Slam titles, was a silver medallist in singles at the 2016 Rio Olympics.
In a first-round clash of mothers, Kerber faces four-time Grand Slam champion Naomi Osaka of Japan.
Women's world number one Iga Swiatek, returning to the scene of her fourth French Open title last month, begins against Romania's Irina-Camelia Begu.
Second-ranked US Open champion Coco Gauff, who missed the Tokyo Olympics three years ago with Covid, takes on Australia's Ajla Tomljanovic.