Germany’s Angelique Kerber prevailed over fifth seed Maria Sharapova to grab her quarter-final ticket.
The ninth seed outlasted the reigning French Open champion in a tense final set, when she converted her seventh match point and win 7-6 6-4 6-4 after two hours 36 minutes.
She will face Canada’s Eugenie Bouchard in the last-eight.
Sharapova joins top seed Serena Williams and second seed Li Na among the favourites to have exited the championship before commencement of the real battle.
“I always consider myself one of the favourites because I’ve won Grand Slams before, been number one in the world,” said Sharapova who won his only Wimbledon title in 2004 as a teenager.
“It’s absolutely normal for people to have high expectations of me doing well in Grand Slam stages. I certainly do, as well. Today could have gone either way, and it didn’t go my way.”
Kerber told BBC Sport: “It’s unbelievable. It was such a tough match, playing to a high level, and it was so close. I’m so happy. She’s a great player on grass, but I was just focusing on myself and I’m happy to be in the quarters.”
Third seed Simona Halep cruised into her third Grand Slam quarter-final of the year as she dispatched off Kazakhstan’s world number 72, Zarina Diyas 6-3, 6-0 after a rain delay had shifted the match from Monday to Tuesday.
Halep, 22, the last of the highest seeds in the women’s draw, next face Sabine Lisicki, who beat another Kazakh, Yiroslava Shvedova, 6-3, 3-6, 6-4 despite getting treatment for a shoulder problem when facing break point.