In the first showdown between Phelps and Australian Ian Thorpe, neither could come out a winner.
South Africa spoiled things for Phelps by winning the relay in a world record 3:13.17. The Netherlands finished second in 3:14.36 and the Americans, with Phelps swimming the second leg, settled for the bronze. Phelps won the 400 individual medley Saturday night.
Thorpe swam the final leg for the Australians, but finished sixth.
Thorpe and Phelps swam in the same heat of the 200-meter freestyle earlier in the day and Thorpe bested Phelps by .43 of a second. They will swim the final of that event Monday night.
Phelps had hoped to break the record of seven gold medals in one Olympics, held by Mark Spitz.
Other swimming winners Sunday night were Australian Petria Thomas in the women's 100 butterfly (57.72), Kosuke Kitajima of Japan in the men's 100 breaststroke (1:00.08) and Laure Manaudou of France in the women's 400 freestyle (4:05.34).