And, in another first, Australian bookmakers offered odds on the outcome of their match with Martina Hingis and Monica Seles because of the sudden interest.
The Williams sisters are quoted favorites at around 7-4 on with Hingis and Seles at 6-5 against.
It is unusual for a women's doubles match to be given top billing at a men's and women's tournament, but even more so when the likes of Australia's own Lleyton Hewitt and Russian Anna Kournikova are in action.
Normally, the two pairs would not have met until the final, but the late decision by the Williams sisters to ask for a wild-card meant they were not seeded and they were drawn to meet first up.
Typically Venus and Serena, who teamed up win Olympic gold on the same court last September, wasted little time adding extra spice to the match by predicting they would win easily.
"It doesn't matter who we play or when we play," Serena said. "Venus and I are on a streak now and we're really hard to beat."
Hingis and Seles, ranked first and fourth respectively in the world in singles, are playing together for the first time after Hingis split from her regular partner, Kournikova.
"I'm looking forward to playing doubles with Martina," Seles said.
"She's No. 1 in the world in singles and obviously has great results in the doubles."