Peng's opener at Roland Garros against Slovakia's Rebecca Sramkova was briefly suspended due to rain when she led 3-1 in the first set.
She continued her momentum to register a 6-3 win, and also stayed ahead in the second set tiebreak.
Then Sramkova, 11 years younger than Peng, made the most of the court with long rallies. Hampered by knee problems, Peng often failed to return the ball as she would have liked. After conceding the tiebreak 7-5, the Chinese veteran had to bow out in the deciding set.
Liu Fangzhou became the other Chinese to be knocked out following a 6-1, 2-6, 6-2 defeat to Japan's Ayano Shimizu.
Wang Xiyu and Lu Jiajing will step onto court for their first round qualifiers in the women's singles on Wednesday, while Zhang Ze will look to find his way into the main draw for the men's singles.
The French Open qualifiers are being played until Friday, with 16 male and 12 female players looking to progress into the tournament proper.
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