
Sharapova 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 the Russian world number one was beaten 6-4 6-3 by German 15th seed Sabine Lisicki on a chilly Court One.
Clijsters, due to retire after the US Open later this year, lost 6-1 6-1 to German eighth seed Angelique Kerber.
At least Federer is still standing, although for a while against erratic Belgian Xavier Malisse that seemed an effort in itself for the six-times champion.
Struggling with a bad back in chilly conditions on Centre Court, the king of cool needed two undignified injury time-outs during a 7-6 6-1 4-6 6-3 victory that continued his remarkable run of grand slam quarter-final appearances.
He remained on course for a semi-final against defending champion Novak Djokovic who thrashed fellow Serb Viktor Troicki 6-3 6-1 6-3.
While the women's quarter-final line-up is complete, five men's fourth-round matches were unfinished due to persistent rain in south west London.
Home favorite Andy Murray must try to finish off Marin Cilic on Tuesday after taking a one-set lead and fifth seed Jo-Wilfried Tsonga will resume a set down against Mardy Fish.
Serena Williams and Petra Kvitova also beat the rain to set up a juicy last-eight clash in the women's singles.
Williams, seeking a fifth Wimbledon singles title to equal the total of her sister Venus, scrambled through to the quarter-finals for the 10th time with a 6-1 2-6 7-5 win over powerful Kazakh Yaroslava Shvedova.
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