The 31-year-old secured his fifth title of city 2016 as he teamed up with Ryan murphy, cody Miller and Nathan Adrian to line a new Games record of 3 minutes 27.95 seconds.
Britain finished 2.71 seconds adrift, with Australia in third. USA additionally successfully defended their title within the women's 4x100m medley. Kathleen Baker, Lilly King, Dana Vollmer and Simone Manuel clocked 3:53.13 to win USA's 1000th gold at a Summer Games.
American legend Michael Phelps won a twenty third Olympic title in his final race at a Games, as nice GB took silver within the men's 4x100m medley relay.
Phelps, meanwhile, bowed out with twenty eight Olympic medals to his name. murphy set the pace within the first leg of the men's race, setting a new backstroke world record of 51.85 seconds, as Britain's Chris Walker-Hebbon finished his stint in sixth.
But a blistering breaststroke leg from 100m gold medallist and world record holder Adam peaty, whose split was 56.59, saw the quickest qualifiers take the lead.
The Americans regained the lead within the butterfly, as Phelps overtook James Guy, and Adrian held off Duncan Scott within the final straight to give the USA their sixteenth swimming gold medal in rio.
With one gold and 5 silvers, it was British swimming's most successful Games since 1908.
Earlier, Fran Halsall claimed Britain's seventh fourth-placed end of the meet within the women's 50m race final, before returning in seventh along side Georgia Davies, Chloe Tutton, Siobhan-Marie o'connor within the women's 4x100m medley relay.
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