Andy Murray, a two-time grand slam champion and Olympic gold medallist, is due to play Australia's Marinko Matosevic with a place in the third round at stake.
Last year's runner-up David Ferrer faces Italian Simone Bolelli while local favourites Gael Monfils and 12th seed Richard Gasquet are also in action.
Serbia's Jelena Jankovic opens proceedings on Philippe Chatrier against Japan's Kurumi Nara before compatriot Ana Ivanovic, winner of the 2008 French Open, faces Ukraine's Elina Svitolina.
(Writing by Tom Hayward, editing by Mark Meadows)
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