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Spain’s Nadal, who has won the men’s title on a record 14 occasions, plans to retire later this year.
Zverev, 27, is one of the favourites for the title and tuned up by winning the Italian Open last week.
Britain’s Andy Murray has also indicated he will call it a day in the coming months and starts against fellow veteran Stan Wawrinka.
Murray, 37, has only played on the Roland Garros clay once since 2017, losing resoundingly in the first round to Wawrinka four years ago.
The Scot returns for the final time after recovering from an ankle injury.
Defending men’s champion Novak Djokovic starts against French wildcard Pierre-Hugues Herbert, while Iga Swiatek begins her bid for a third women’s title in a row against a qualifier or lucky loser.
The French Open, which is the second Grand Slam tournament of the season, starts on Sunday, 26 May.