Since their 2001 US Open final, which Venus won in straight sets, Serena has won all five of their meetings in Grand Slam finals, including Wimbledon in 20.
In winning her "Serena Slam" – the four Grand Slam tournaments in succession from the 2002 French Open – Serena beat Venus in all four finals.
"I never expected a medal - gold, silver or bronze," said Dementieva, 26, a runner-up at the French and US Opens in 2004. "Having three Russian girls left standing in the Olympics is a huge moment for Russia," Dementieva said.
"I know we were expecting and planning for some medals but I don't think anyone could expect three medals from the girls." In the women's doubles, 2000 champions Serena and Venus Williams won their second career gold with a one-sided 6-2 6-0 victory over Spain's Anabel Medina Garrigues and Virginia Ruano Pascual.
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The third sister showdown final at Wimbledon was confirmed when Serena overcame China's Zheng Jie 6-2, 7-6, Venus having beaten Dementieva 6-1, 7-6 earlier in the afternoon.
The final line-up ensures an extension of the sisters' remarkable domination here, Venus having won four of the last eight All England Club championships and Serena two.