The 90th ranked Nara, who beat 15-year-old Amanda Anisimova in three tight sets, will take on a player more than two decades older in the opening match on the main Philippe Chatrier showcourt on Wednesday.
The 25-year-old from Osaka got the better of seven-times grand slam singles champion Williams, who turns 37 next month, in straight sets the last time they met on the hard courts of Indian Wells in 2016.
Nara has failed to set pulses racing so far this year, however, the highlight of her season being a win over Serbia's Jelena Jankovic in Taipei.
Tenth seed Williams, meanwhile, has a relatively modest record on the Paris clay, with only two quarter-final runs to her name since losing to sister Serena in her only French Open final in 2002.
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(Reporting by John Stonestreet; Editing by Peter Rutherford)
