The US had a half-second lead going into Ryan Lochte's final leg, but French specialist Yannick Agnel overtook him on the final straight to claim the gold in 3 minutes 9.93 seconds.
The Americans, who were 0.7 seconds ahead after Michael Phelps' second leg, were half a second behind for silver, while Russia stole the bronze, leaving the Australians out of the medals in fourth.
France's trio of Amaury Leveaux, Fabien Gilot and Clement Lefert held the country in third behind the Americans and Australians in the first three legs, before Agnel's turbo 100.
The US fielded Nathan Adrian for the first leg, Phelps on the second, returning with Cullen Jones and then Lochte.
Russia put out a talented team including Beijing silver medallist Nikita Lobintsev, who was joined by Andrey Grechin, Vladimir Morozov and Danila Izotov.
Izotov outpaced Australia's James Roberts to bring home the bronze on the final leg.
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