The top seed is just seven wins away from becoming only the third man to hold all four majors at the same time.
But the Wimbledon, US Open and Australian Open champion has never made a final in Paris, falling at the semi-finals on three occasions.
He also has Roger Federer in his half of the draw where the great Swiss looms as a potential semi-final opponent.
Federer, the holder of a record 16 Grand Slam titles, was the champion at Roland Garros in 2009, and he also starts his campaign on Monday against Germany’s Tobias Kamke.
Defending women’s champion Li Na of China is second match on Philippe Chatrier Court where she faces Romania’s Sorana Cirstea.
Top seed and world number one Victoria Azarenka, the Australian Open champion, begins proceedings on the main court against Alberta Brianti of Italy.
Former men’s world number one Lleyton Hewitt of Australia is also in action against Slovenia’s Blaz Kavcic.
The former Wimbledon and US Open champion will take to Court Seven with two screws and a metal plate now locking permanently into place in the big toe on his left foot after undergoing radical surgery to prolong his career.
Hewitt, now ranked 175, has had only two weeks of practice ahead of his first-round match and if he gets past Kavcic his next opponent could be Djokovic.