The Serbian top seed will be second on Court Philippe Chatrier after local favourite Marion Bartoli, the 13th seed, opens proceedings against Belarusian Olga Govortsova.
Perhaps because of superstition, Djokovic has requested his team and reporters to make no mention of future rounds.
There will be a veterans' day feeling as the 42-year-old Kimiko Date Krumm takes on Australian ninth seed Samantha Stosur on Court One and German 12th seed Tommy Haas, 35, is up against France's Guillaume Ruffin on Court Suzanne Lenglen, where all four matches feature French players.
Marathon man Nicolas Mahut, who played the longest professional tennis match at Wimbledon in 2010, is scheduled on Court Philippe Chatrier against Serbian eighth seed Janko Tipsarevic.
Last on centre court will be Belarusian Victoria Azarenka, the third seed, who is looking to clinch a third Grand Slam title after winning the last two Australian Open titles.