Swiss Federer, the third seed, hopes to capture a record 17th grand slam title to his collection when he starts his campaign on Court Suzanne Lenglen against German Tobias Kamke.
World number one Djokovic, who will become the first man in 43 years to hold all four grand slams simultaneously if he wins his maiden French Open crown, will be on Court Philippe Chatrier against Italian Potito Starace.
Opening proceedings on centre court will be world number one Victoria Azarenka against Italy's Alberta Brianti as the Belarussian looks to cement her place at the top of the WTA rankings.
Defending champion Li Na of China, seeded seventh, will be back on her favourite court against Romanian Sorana Cirstea.
Local favourite Arnaud Clement, the oldest player in the men's draw at 34 who is set to retire at the end of the season, will be starting his last French Open against Russian Alex Bogomolov Jr.