American Williams, 36, has not played a major tournament since winning a 23rd title at the 2017 Australian Open, having given birth to her daughter Alexis in September.
World number one Simona Halep, chasing a maiden grand slam crown, will start her campaign against American Alison Riske.
In the men’s draw, third seed Marin Cilic takes on Australian James Duckworth.
Defending champion Rafa Nadal will look to wrap up his first-round match against Italian Simone Bolelli after rain halted play on Monday evening. The Spaniard leads 6-4 6-3 0-3.
Order of play on the main show courts (all matches first round, times AEST, prefix numbers denote seeding):
Philippe Chatrier (play starts at 1900 AEST with SBS live from 2200 online and 2230 on TV)
3-Marin Cilic (Croatia) v James Duckworth (Australia)
1-Rafael Nadal (Spain) v Simone Bolelli (Italy) (Nadal leads 6-4 6-3 0-3)
Kristyna Pliskova (Czech Republic) v Serena Williams (U.S.)
Jeremy Chardy (France) v 17-Tomas Berdych (Czech Republic)
1-Simona Halep (Romania) v Alison Riske (U.S.)
Suzanne-Lenglen (play starts at 1900 AEST with SBS live from 2200 online and 2230 on TV)
24-Denis Shapovalov (Canada) v John Millman (Australia)
28-Maria Sharapova (Russia) v Richel Hogenkamp (Netherlands)
Duan Yingying (China) v 7-Caroline Garcia (France)
Nicolas Mahut (France) v 5-Juan Martin Del Potro (Argentina)
Court One (play starts at 1900 AEST with SBS live from 2200 online and 2230 on TV)
3-Garbine Muguruza (Spain) v Svetlana Kuznetsova (Russia)
Steve Johnson (U.S.) v 25-Adrian Mannarino (France)
11-Julia Goerges (Germany) v Dominika Cibulkova (Slovakia)
Leonardo Mayer (Argentina) - Julien Benneteau (France)