The top-seeded Djokovic's foe will be Potito Starace and Nadal will go against Simone Bolleli.
Neither Italian has won an ATP singles title.
The draws were announced Friday, two days before the start of the season's second Grand Slam event.
Potential opponents on Djokovic's side of the draw include third-ranked Roger Federer and Jo-Wilfried Tsonga, who is world No. 5.
A win for Djokovic would give him his first French Open title and his fourth straight Grand Slam championship. The other three were Wimbledon and the U.S. Open last year and the Australian Open, this year's first major.
Federer, who has won 16 Grand Slam tournaments, including the 2009 French Open, will begin the tournament against Germany's Tobias Kamke.
Murray drew Tatsuma Ito of Japan in the first round.
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