Former world number one Caroline Wozniacki followed 2010 champion Francesca Schiavone out of the French Open after losing to Kaia Kanepi.
Ninth seed Wozniacki was beaten 6-1 6-7 (3-7) 6-3 by 25-ranked Kanepi, while Schiavone went down 3-6 6-3 8-6 to Varvara Lepchenko of the United States.
Defending champion Li Na, seeded seventh,and second seed Maria Sharapova both progressed.
Sharapova will complete a career Grand Slam if she wins the tournament.
Wozniacki had looked set for a straight sets defeat as Kanepi led 5-3 in the second set.
But the 21-year-old Dane fought back from match point down by claiming 10 points in a row before taking the set after a 76 minute battle, forcing the game into a decider.
Kanepi held firm in the final set to join Li and Sharapova in the fourth round, where she will play Arantxa Rus who won 7-6 (7-5) 2-6 6-2 against Julia Goerges.
Sharapova's passage was considerably easier as the 25-year-old Russian beat China's Peng Shuai 6-2 6-1.
She will play Klara Zakopalova, who beat Anastasia Pavlyuchenkova 6-3 7-5, in the last 16.
"I'm certainly happy with the way I performed in those rounds, in those matches, and followed through. I did everything I had to do," said Sharapova, who will return to the top of the world rankings if she lifts the Suzanne Lenglen Cup next Saturday.
"But in the next round, it starts from 0-0. Whoever you're playing, you have to go and try and do the same thing.
"There are a lot more rounds to go. It just gets tougher from this point. And you hope as the tournament goes on that you raise your level, that you get better."
Seventh seed Li battled back from a set down to secure a 3-6 6-2 6-1 victory over American Christina McHale and will play Yaroslava Shvedova in the next round.
World number 142 Shvedova made it to the second week with a 6-4 7-5 win against Spain's Carla Suarez Navarro.
"In the first set, I just followed her [McHale]. In the second set I was able to play my way," said Li.
"McHale is a dangerous player. I am happy to win because I had more experience."
Lepchenko's victory over Schiavone strengthens her chances of qualifying for the United States team for the London Olympics as she is expected to move above Venus Williams in the world rankings because of the win.
Williams's place at the Olympics in serious doubt because she lost in the second round while Sloane Stephens, who is currently ranked lower than the former world number one, is still in the tournament.
Lepchenko will play fourth seed Petra Kvitova in the last 16 and should she win, she will be guaranteed her place at the Games.