1 seeds at the Western & Southern Open — advanced with straight-set wins on Wednesday, while the rest of their brackets suffered more top losses.
Nadal sat out an hour-long rain delay and beat Richard Gasquet 6-3, 6-4 on Wednesday night, finishing it off with two of his eight aces.
Pliskova needed only 67 minutes to get a 6-2, 6-3 win over Natalia Vikhlyantseva, a solid showing as the defending champion.
Williams is enjoying a comeback season, reaching the finals at the Australian Open and Wimbledon at age 37.
The men's bracket is without Roger Federer, Andy Murray, Novak Djokovic and defending champion Marin Cilic because of injuries.
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