Fifth seed Serena Williams crashed out of the French Open on Friday losing a third round tie 6-4, 6-4 to Katarina Srebotnik of Slovenia.
The 27th seed will play the winner of the match between Emilie Loit of France and Patty Schnyder of Switzerland for a place in the quarter-finals.
Williams looked out of sorts from the start quickly falling a service break down as the 27-year-old Srebotnik, who had lost her three previous meetings against the American, cleverly mixed her shot-making.
It was a similar story in the second set as Williams, the 2002 champion here when she beat sister Venus in the final, hung on grimly only to drop her serve again in the ninth game.
Srebotnik let two match points slip by at 40-15, but clinched it on the next one as Williams hit a looping forehand wide.
It was the biggest win of Dubai-based Srebotnik's career taking her into the last 16 at Roland Garros for only the second time in 10 attempts.
For Williams it was the first time she had gone out of a Grand Slam tournament so early since the 2006 Australian Open.
Sister Venus, the eighth seed, was scheduled to play the last match on the Philippe Chatrier Centre Court against Italian claycourter Flavia Pennetta who beat her in Bangkok last year the last time they played.