Spain’s Nadal, 38, had cast doubt on whether he would even be able to play against Hungary’s Marton Fucsovics because of a thigh injury.
But the 2008 gold medallist had enough to see off Fucsovics in a 6-1 4-6 6-4 win.
Nadal, playing at the scene of his record 14 men’s singles titles, returned to Court Philippe Chatrier less than 24 hours after he played alongside Carlos Alcaraz in the men’s doubles.
A superb first set against Fucsovics initially allayed any fears about his physical state, although he was unable to keep up that level in the second.
With his thigh heavily strapped, Nadal fought back in the decider and scrapped through to victory with the trademark tenacity which he demonstrated throughout his career.
Nadal goes on to face Djokovic later this week as the pair extend their enduring rivalry to a 60th meeting.
Serbia’s Djokovic, 37, advanced to the second round with a simple success over Australia’s Matt Ebden on Saturday.
He and Nadal are two of the greatest players of all-time, having won a combined 46 Grand Slam singles titles – tipped 24-22 in Djokovic’s favour – and set countless records which may never be broken.
Nadal hinted last year that 2024 might be his final season on the tour and, although he has since rowed back somewhat, it still remains to be seen how long he will continue after a series of injury problems in the past two years.
Djokovic is a year younger but still contesting the sport’s most prestigious prizes and bidding for the one thing which still eludes him – Olympic gold.