Sharapova, who needs to win the title and rely on Serena Williams not reaching the final in Singapore to overtake the American for top spot, fell to a 0-2 record while Kvitova is 1-1 in the White Group round-robin stage.
In order for Sharapova to progress to the semifinals, she will need to win her last match against Agnieszka Radwanska and rely on Caroline Wozniacki beating Kvitova, and have both matches decided in straight sets.
Kvitova said she was feeling burnt out during her first-round loss to Radwanska, so took an unusual approach to freshen up for Thursday's match.
"When I lost against Aga ... I was so tired and sick of the tennis for a moment," Kvitova said. "So I didn't practice today at all and I just really relaxed and cleaned my mind a little bit."
"I didn't feel as sharp as I did in the previous matches against her," Sharapova said. "I just don't feel that I reacted as well in her bigger shots. She's someone that likes to play aggressive and hit the ball, and very deep as well. She countered my shots extremely well and I was just never ready for the next ball.
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