Maria Sharapova, the top seed and bookies favourite to regain the Wimbledon title she won as a 17 year old in 2004, suffered a shock straight sets defeat at the hands of Sabine Lisicki, a player she hasn't lost to in three previous meetings, including last year's semi-final at The Championships.
The 6-4 6-3 scoreline reflected the powerful approach of the German, seeded 15, who never wavered despite some heavy pressure from the Russian's relentless screeching .
The loss also means that Sharapova could well find herself replaced at the top of the women's rankings come next Monday.
The other favourite favoured by the bookies, Serena Williams, suffered the ignominy of dropping a set for the second successive round, but managed somehow to recover and get past Yaroslava Shvedova, the Kazhakstani who had scored the Golden Set on Saturday, 6-1 2-6 7-5.
However another marquee player, and a favourite of the crowds, Kim Clijsters, brought her Wimbledon career to an end. Unfortunately for the Belgian, the manner of her dismissal wasn't what she would have hoped for winning just two games against Angelique Kerber, the eighth seed from Germany who now goes on to face her compatriot Lisicki for that semi-final place.
Defending champion Petra Kvitova also came under considerable pressure against Francesca Schiavone who claimed the opening set before capitulating to the more powerful Czech 4-6 7-5 6-1 in a match disrupted somewhat by rain to the frustration of the Italian 24th seed.
There were no problems for Agnieska Radwanska who is emerging as a dark horse for the title, the unseeded Tamira Paszek, the Eastbourne champion and the second seed, Victoria Azarenka.
Individual reports below
Sabine Lisicki bt Maria Sharapova (6-4 6-3)
The Russian world number one had been bidding to become the first player since Serena Williams in 2002 to win the French Open-Wimbledon double in the same year but was undone by a stream of unforced errors in a rain-disrupted match on Court One.
She lost 6-4 6-3 to Sabine Lisicki, the 15the seed, who avenged last year's semi-final defeat by outplaying the top seed with a 6-4 6-3 fourth round victory over the world No. 1.
The 25-year-old Russian has been a finalist in three of the last four Grand Slams and arrived at Wimbledon on a high after winning the French Open for the first time earlier this month.
But she was brought down to earth with a bump on Court One as Lisicki, beaten in the first round in her four pre-Wimbledon tournaments, produced one of the best performances of her career.
Lisicki will now play her country woman, the eighth seed Angelique Kerber, for a place in the last four.
"It's just unbelievable. I'm so happy. I had lost the last three meetings with her, so it's nice to finally win one," Lisicki said.
"I just went for my shots out there. I felt great, it's my favorite tournament. I love the crowd and playing on grass.
"I'm a fighter and I fight to the last game. I think I'm getting better with each match."
The warning signs had been there for Sharapova, who won Wimbledon as a 17-year-old in 2004, as she hadn't been at her dominant best in the first week.
She had to survive a hard-fought clash with Tsvetana Pironkova before finally winning in three sets in the second round and it soon became clear Lisicki, pumped up to avenge last year's defeat, would pose her plenty of problems.
Lisicki has always thrived at Wimbledon, reaching the last four as a wild card last year and making a quarterfinal appearance in 2009.
The big-hitting 22-year-old, dubbed "Doris Becker" by German media for her powerful style, was quickly into her stride and broke for a 3-1 lead in the first set.
Even when nerves got the better of Lisicki as she served for the set, allowing Sharapova to break, it was the German's response that impressed as she came out all guns blazing and broke straight back to take the set at the second attempt.
Rain halted play with Sharapova 30-15 up on Lisicki's serve in the first game of the second set.
But the 45-minute delay did little to improve Sharapova's mindset and a double-fault presented Lisicki with two break points, which the German gratefully converted at the first attempt with a blistering forehand return.
China's Li Na once described Lisicki as "serving like a man" and the German was keeping Sharapova firmly on the back foot with her howitzer deliveries.
Sharapova is usually able to hit her way out of trouble against most opponents, but she was rendered increasingly impotent by Lisicki's power play.
When it came to serve for the match, Sharapova might have hoped for Lisicki to crack under pressure.
The German squandered one match point with a miscued forehand and couldn't take her second either, but a huge second serve ace sealed victory and she fell to her knees in jubilation.
Serena Williams bt Yaroslava Shvedova (6-1 2-6 7-5)
Serena Williams again went the distance, but again came out victorious with a hard-fought, fourth-round victory over Kazakhstan's Yaroslava Shvedova at Wimbledon.
Williams had to rally from a set down to beat China's Zheng Jie in the third round on Saturday, prevailing 9-7 in the decisive set, and went deep into the third set Monday to dispose of Shvedova, advancing to the quarterfinals with a 6-1 2-6 7-5 triumph.
The four-time Wimbledon champion breezed through the first set on a cold and rainy Monday in 26 minutes, but Shvedova, who played a "golden set" by winning every point in the first set of her third-round win over French Open runner-up Sara Errani on Saturday, had an answer with a dominant second set in 34 minutes.
As rain picked up and other courts stopped play, Court No. 2 remained active and the third set remained on serve until late.
Williams picked up three break points in the ninth game, only to watch Shvedova save all three and hold. In the 11th game, Williams again earned a pair of break points and needed only one to convert when Shvedova's backhand went wide.
Shvedova, though, fought through the next game and thought she'd hit a winner on a brilliant angle that would have given her a break point. Williams, though, ran it down and lifted a perfect lob to instead set up a match point, which she quickly converted by drilling a backhand that went unreturned.
Williams will next face the winner defending champion Petra Kvitova.
Petra Kvitova bt Francesca Schiavone (4-6 7-5 6-1)
Defending champion Petra Kvitova came back from a set and a break down to beat Italian Francesac Schiavone 4-6 7-5 6-1 in a rain-disrupted fourth-round match on Monday.
Kvitova, the fourth seed, looked to be in trouble when former French Open champion Schiavone went a set and 2-1 up, taking advantage of a double fault to help her break the Czech.
Kvitova, however, broke straight back and went 6-5 up before light rain began falling on Court Three.
The match continued after a series of stops and starts, with the players sitting on their chairs, wrapped in towels and sheltering under umbrellas, while officials waited to see if the rain would stop.
Schiavone was clearly unhappy at being told to resume play early in the third set, complaining to no avail that the grass was damp and slippery.
As Kvitova stood waiting to play, British umpire Fiona Edwards urged Schiavone back on to the court, saying: ""Can we at least try? I will watch you."
The Italian relented but she continued to glower and mutter as Kvitova raced through two breaks of serve to wrap up the set in 39 minutes, finishing off with a love game.
Schiavone later revealed she had been unhappy at the indecisiveness of the umpire.
"When it is damp you should say yes or no, not just stay there and wait," she told a news conference. "But that is not an excuse (for losing), of course.
"I am sorry because I knew how I was playing," she added. "I knew how much this match counted. I was playing a good game, I was winning."
Kvitova sympathised with Schiavone but said she had been keen to play on despite the weather.
"The grass was a little bit damp so it was a little bit dangerous but I was ready to play on, to continue, because I knew that I had a chance," she said.
"When I made the break finally, after one hour or however long we had played, it was better for me."
Kvitova, who had not dropped a set in the first three rounds, will now face former champion Serena Williams.
"I think it will be a huge match for both of us," Kvitova said of the quarter-final scheduled for Tuesday, weather permitting. "I am looking forward to facing her and looking forward to having a challenge."
Angelique Kerber bt Kim Clijsters (6-1 6-1)
Kim Clijsters waved goodbye to Wimbledon on Monday after she was thrashed 6-1 6-1 by German eighth seed Angelique Kerber at a windswept and chilly All England Club on Monday.
The Belgian, who will be retiring for a second time after this year's U.S. Open, looked like a pale shadow of the player who has won four major titles. She struggled to get her serve into gear and committed a string of unforced errors.
Kerber was in sparkling form and totally dominated the exchanges against crowd favourite Clijsters, who was suffering from an abdominal injury in the lead-up to Wimbledon.
Clijsters survived two match points at 5-0 down in the second set but it was a last throw of the dice against the fiercely determined Kerber who served out for victory.
At least one German player is guaranteed a place in the semi-finals after Kerber booked a last-eight date with compatriot Sabine Lisicki.
Tamira Paszek bt Roberta Vinci (6-2 6-2)
The first woman to advance to the quarterfinals was Austria's Tamira Paszek, who rolled to a 6-2 6-2, 63-minute victory over Italy's Roberta Vinci. Paszek, a quarterfinalist last year at the All England Club and this year's Eastbourne champion, will next meet the second seed Victoria Azarenka.
Victoria Azarenka bt Ana Ivanovic (6-1 6-0)
Second seed Victoria Azarenka crushed Ana Ivanovic 6-1 6-0 in just over an hour to reach the Wimbledon quarter-finals on Monday.
Belarussian Azarenka completely outclassed the former French Open champion, seeded 14th, moving her relentlessly around the court with a succession of accurate and powerful groundstrokes.
Azarenka's main problem in the second set was a pigeon trapped under the Centre Court roof but she calmly removed a few feathers which fluttered on to the playing surface before resuming her impressive performance that included only six unforced errors.
The Australian Open champion sealed victory when Serb Ivanovic netted a backhand and will play Austrian Tamira Paszek in the last eight.
In the final two matches, Agnieska Radwanska beat qualifier Camila Giorgi (6-2 6-3) and Maria Kirilenko squeezed past Shuai Peng (6-1 6-7(6) 6-3).