Wawrinka, like Li the reigning Australian Open, lost in the first round on Monday.
Danish former world No.1 Wozniacki's engagement to Rory McIlroy was called off by the golfer last week and the 13th seed is sure to face questions about the split after she plays Yanina Wickmayer of Belgium in the third match on court three.
Simona Halep of Romania, a rising force in women's tennis and seeded fourth here, opens the day on the Philippe Chatrier show court against Alisa Kleybanova of Russia.
Wimbledon champion Andy Murray takes on Andrey Golubev of Kazakhstan in the third match on Suzanne Lenglen while 15th seed Sloane Stephens of the U.S. will play her rain-postponed match against China's Shuai Peng second up on Court One.
Kimiko Date-Krumm, the 43-year-old Japanese, plays 24th seed Anastasia Pavlyuchenkova of Russia -- one of 66 women in the draw who were not even born when she turned professional.
After rain disrupted play on Monday, the grand slam tournament's second day, and forecasters expect few problems on Tuesday before the rain returns later in the week.
(Reporting By Robert Woodward; editing by Martyn Herman)
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