The Williamses climbed to No. 1 in doubles for the first time after winning the French Open. They were bidding for their 13th major championship.
Serena, who will play in the singles semifinals Thursday, wore a bandage on her right shoulder. Zvonareva is in the singles semifinals for the first time, and they could meet in the final.
The match turned when Venus double-faulted on break point in the second set, giving the Russians a 4-2 lead. Serena lost serve in the third game of the final set, and the sisters didn't manage a break in the last two sets.
The defeat was only the fifth in 60 matches for the Williamses in the past three years. They fell to 29-2 at Wimbledon. - AP