American Williams, who is bidding for an 18th grand slam singles title to move alongside Chris Evert and Martina Navratilova, is third on Court Philippe Chatrier in what is likely to be a chilly, and possibly rainy day in Paris.
"We were talking about it before the draw was made. It's ironic, I guess. It is what it is," the 32-year-old, a huge favourite after winning the Rome title last week, told reporters after discovering her first opponent.
Before her on centre court is Swiss crowd favourite Roger Federer, who takes on unheralded Slovakian Lukas Lacko as he looks to add to his record 17 grand slam titles having not won a major since Wimbledon 2012.
Closing proceedings will be Jo-Wilfried Tsonga, probably France's best hope for a men's champion, against compatriot Edouard Roger Vasselin.
"I expect a lot from me, especially here," Tsonga said.
"I know it's always a lot of pressure, but I think now I have enough experience. I played a few times Roland Garros. I know how it is."
(Reporting by Julien Pretot; Editing by Martyn Herman)
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