Second seed, Li Na, was beaten 7-6 (7-5) 7-6 (7-5) by Barbora Strycova in the third round of the women’s singles.
China’s Li was badly out of sorts against her Czech opponent, who will play 16th seed Caroline Wozniacki next.
Australian Open champion Li, 32, has not advanced beyond the third round in eight appearances at Wimbledon and lost in the first round at this year’s French Open.
Former world number one Caroline Wozniacki reached round four with a 6-3 6-0 defeat of Croatia’s Ana Konjuh.
Romania’s third seed, Simona Halep, runner up at this year’s French Open, reached round three with a 6-3 4-6 6-4 victory over Ukraine’s Lesia Tsurenko.
Twenty-two year old, Halep will play world number 71 Belinda Bencic next after the Swiss player beat American Victoria Duval 6-4 7-5.
Russian Ekaterina Makarova, seeded 22, also reached the fourth round with a 7-5 6-3 defeat of France’s Caroline Garcia.
In the men category, top seed Novak Djokovic moved into the fourth round of the men’s singles with a comfortable 6-4 6-2 6-4 defeat of Frenchman Gilles Simon despite injury scare.
The world number two will play 14th seed Jo-Wilfried Tsonga next after the Frenchman beat Jimmy Wang 6-2 6-2 7-5.
Djokovic was leading 3-2 in the third set and seemingly closing in on an uneventful victory when he dived to reach a forehand and appeared to twist his left arm.
The 2011 champion looked in extreme pain but a trainer manipulated his shoulder and the 27-year-old was able to continue.
South Africa’s Kevin Anderson beat 16th seed Fabio Fognini in five sets.
Anderson, the 20th seed, won 4-6 6-4 2-6 6-2 6-1 and will play Britain’s Andy Murray in round four, if the defending champion wins his third-round match against Roberto Bautista Agut.