Despite clinching the opening set convincingly, the Indian pair failed to counter the spirited fightback from Rajeev and Venus in the second set of a magnificent tennis match.
The American pair subsequently carried their new-found confidence into the tiebreaker and blew away the Indian duo 10-3 in the decisive set to eventually claim a 2-6, 6-2, 10-3 win over Sania and Rohan.
Sania and Bopanna will next play the loser of the match between Czech Republican pair of Radek Stepanek-Lucie Hradecka and American duo of Jack Sock-Bethanie Mattek-Sands in the bronze medal playoff on Sunday.