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Lisicki, who plays Estonia's Kaia Kanepi for a place in the last four, has an impressive Wimbledon record, reaching the quarter-finals three times and the last four in 2011, but this incredible upset on Centre Court was by far her greatest achievement at the All England Club.
The 23-year-old has failed to make it past the fourth round in 16 Grand Slam appearances outside Wimbledon, but she comes alive on the grass-courts of south-west London.
"I'm still shaking, I'm so happy", said Lisicki, breaking into tears.
"Serena played a fantastic match. She's such a tough opponent and it's just an amazing feeling to win.
"The crowd was so amazing. I love this court so much, it's such a special place for me.
"I did enjoy it. She played some unbelievable shots. I was just fighting for every single point and hanging in there.
Her
remarkable victory was no fluke.
Despite facing the most ferocious hitter in the history of women's tennis, Lisicki matched Serena blow for blow, unloading more winners and serving more aces than the five-time Wimbledon champion in two hours and four minutes of high drama.
In a tournament most memorable this year for the fall of its biggest stars, this was arguably the most astonishing result of all.
Since an embarrassing first round loss against Virginie Razzano at last year's French Open, Williams had simply been unstoppable, winning 77 of her 80 matches and collecting the Wimbledon, US Open, French Open and Olympic titles in the process.
The 31-year-old, a 16-time Grand Slam champion, had swept through the first week, dropping just 11 games in her opening three matches to extend her winning run to 34 matches.
But Lisicki's game is perfectly suited to grass and right from the start it was clear she was capable of upsetting the odds as she earned a break point in the fourth game of the match.
Serena saved it, unleashing a shrieked 'come on' that suggested she was well aware of the threat.
Lisicki wasn't deterred and she kept the pressure on Williams, earning another break point in the sixth game which she converted when the American blazed a forehand wide.
Serena appeared rattled, gesticulating to her French coach Patrick Mouratoglou and swiping at the turf in frustration as Lisicki punished another shaky service game.
By the time Lisicki closed out the set, she had won four games in a row.
Serena hit back, breaking to love in the third game of the second set during a run of 14 successive points for the American.
She took the set with two more breaks and by the time Williams moved into a 3-0 lead in the deciding set she had won nine consecutive games.
But Williams' concentration wavered with the finish line in sight, allowing Lisicki a lifeline as the German broke in the fifth game.
Even when Williams' broke straight back, Lisicki wouldn't surrender and another break from the German made it 4-4.
Incredibly, Lisicki was back on top and she broke for a 5-4 lead when Williams sent a smash just beyond the baseline.
Lisicki couldn't convert her first match point, sending a forehand long. A double-fault then gifted Serena a break-point, but the German saved it with an ace.
Another big serve brought Lisicki a second match point and this time she seized her chance, finishing off an epic upset with a flashing winner.
Earlier, Kanepi ended Britain's dreams of a first woman in the Wimbledon quarter-finals for 29 years were shattered on Monday when she knocked out the home favourite Laura Robson in the fourth round.In a closely-fought match, Kanepi just had the edge in the crucial points to win 7-6 (8/6), 7-5.
Robson was bidding to become the first British woman to reach a Grand Slam quarter-final since Jo Durie at Wimbledon in 1984.
The 19-year-old left Court One in tears as Kanepi celebrated.
Results from the seventh day of Wimbledon (x denotes seeded player):Men's singles:
Fourth round:
Novak Djokovic (SRB x1) bt Tommy Haas (GER x13) 6-1, 6-4, 7-6 (7/4)
Tomas Berdych (CZE x7) bt Bernard Tomic (AUS) 7-6 (7/4), 6-7 (5/7), 6-4, 6-4
David Ferrer (ESP x4) bt Ivan Dodig (CRO) 6-7 (3/7), 7-6 (8/6), 6-1, 6-1
Juan Martn Del Potro (ARG x8) bt Andreas Seppi (ITA x23) 6-4, 7-6 (7/2), 6-3
Lukasz Kubot (POL) bt Adrian Mannarino (FRA) 4-6, 6-3, 3-6, 6-3, 6-4
Jerzy Janowicz (POL x24) bt Jurgen Melzer (AUT) 3-6, 7-6 (7/1), 6-4, 4-6, 6-4
Fernando Verdasco (ESP) bt Kenny De Schepper (FRA) 6-4, 6-4, 6-4
Andy Murray (GBR x2) bt Mikhail Youzhny (RUS x20) 6-4, 7-6 (7/5), 6-1
Women's singles:
Fourth round:
Sabine Lisicki (GER x23) bt Serena Williams (USA x1) 6-2, 1-6, 6-4
Kaia Kanepi (EST) bt Laura Robson (GBR) 7-6 (8/6), 7-5
Agnieszka Radwanska (POL x4) bt Tsvetana Pironkova (BUL) 4-6, 6-3, 6-3
Li Na (CHN x6) bt Roberta Vinci (ITA x11) 6-2, 6-0
Sloane Stephens (USA x17) bt Monica Puig (PUR) 4-6, 7-5, 6-1
Marion Bartoli (FRA x15) bt Karin Knapp (ITA) 6-2, 6-3
Petra Kvitova (CZE x8) bt Carla Surez (ESP x19) 7-6 (7/5), 6-3
Kirsten Flipkens (BEL x20) bt Flavia Pennetta (ITA) 7-6 (7/2), 6-3
