Kirilenko, the tournament's No. 2 seed, fell to Karin Knapp 1-6, 6-1, 7-5. Knapp piled up six breaks over the second and third sets. Kirilenko dominated the opening set, but Knapp turned it completely around in the second and held on with a late break in the third.
Silvia Soler-Espinosa edged Medina Garrigues 3-6, 6-3, 7-5. She tied the match with one break in the second set and took the seesaw third with three breaks.
Fifth-seeded Zheng Jie was also an upset victim, falling 6-4, 6-1 to Galina Voskoboeva.
No. 1-seeded Roberta Vinci had no problem gaining her quarterfinals berth, dispatching Maria Joao Koehler 6-2, 6-0 in 59 minutes. Vinci won nearly two-thirds of the points in the match.
Petra Cetkovska, the No. 4 seeded, beat Heather Watson 6-3, 6-1 while sixth-seeded Kaia Kanepi got by Vania King 6-3, 6-4 and No. 7-seded Nadia Petrova advanced when Jarmila Gajdosova retired after losing the first set.
Vinci will go against Petrova while Kanepi draws Cetkovska in two of Thursday's quarterfinals. Suarez Navarro plays Soler-Espinosa and Knapp takes on Voskoboeva in the others.