The shock defeat will reopen the debate about the Madrid Open's use of blue clay.
Last year the Spanish capital's experiment with blue clay proved unpopular with most players, and it was banned for this season.
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Tipsarevic had knocked out fellow Serb Djokovic a day earlier, taking advantage of his compatriot's dislike of the blue clay surface.
We need serious discussion about the future of this blue clay.
The clay court season now looks towards the start of the Madrid Open on Monday, which has caused controversy over its use of blue clay for the first time.
Ironically it was Nadal that refused to be drawn on the issue of the blue clay after he had comfortably beaten Russia's Nikolay Davydenko in straight sets 6-2 6-2 on Wednesday.
Any Americans still uncomfortable on the red clay will feel more at home: For the first time, Madrid will be using blue clay, much like the color of the U.S. Open courts.
"I never was in control of the match, I didn't know how to win a point, " Nadal told reporters, before suggesting he will not show up next year unless the controversial blue clay surface is changed.
Williams won last year's event when it was held on blue clay -- an unpopular experiment that was later banned by the tennis authorities -- but she has not played in a final on red dirt since 2002.
Nadal, like Novak Djokovic, couldn't wait to get away from the controversial blue clay at the Caja Magica but Federer has made the best of the situation and thrashed Janko Tipsarevic 6-2, 6-3 on Saturday in a one-sided semifinal.
Her older sibling Venus beat Romania's Simona Halep in the first round for the second tournament in a row, and the 1999 Rome champion will take on Russia's Ekaterina Makarova as she seeks to improve on her second-round defeat on the blue clay last week.
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