Second seed Li Na suffered a surprise defeat by Russia's Elena Vesnina in the quarter-finals of the Aegon International in Eastbourne.
The second seed lost 7-6 (7-4) 6-3 to Vesnina, who had knocked Britain's Heather Watson out of the competition.
Vesnina, the world number 36, needed one hour and 40 minutes to overcome the 2011 French Open champion.
Elsewhere, Caroline Wozniacki set up a semi-final tie with Jamie Hampton after beating Ekaterina Makarova 4-6 6-0 6-3.
"I'm feeling pretty good," said the Dane. "I feel like I have been playing really good tennis.
"She came out playing aggressively, playing well. But I found my game to make it a good match."
American Hampton advanced to the last four thanks to a 3-6 7-6 (7-1) 6-4 victory over Czech Republic's Lucie Safarova.
The qualifier, who defeated top seed Agnieszka Radwanska on her way to the last eight, became the first American since Jennifer Capriati in 2003 to reach the last four in Eastbourne.
Vesnina will next play Yanina Wickmayer, who beat sixth seed Maria Kirilenko 6-2 1-6 7-5.
In the men's draw, second seed Gilles Simon defeated Australia's Bernard Tomic 7-6 (10-8) 6-3 to earn a place in the semi-final against 2011 champion Andreas Seppi.
Seventh seed Seppi overcame Czech Republic's Radek Stepanek 6-4 6-2.
Fernando Lopez came out on top of an all-Spanish tie by beating Fernando Verdasco 6-4 7-6 (8-6).
Lopez will meet the unseeded Ivan Dodig in the semi-finals after the Croatian beat eighth seed Fabio Fognini 6-3 6-2.