Grand Slam singles champions Li Na and Petra Kvitova lead China and Czech Republic into the eight-team Hopman Cup which begins Saturday.
Li, who won this year's French Open, will face Marion Bartoli of France in the tournament's opening match Saturday at Burswood Dome.
France's Richard Gasquet takes on Wu Di in men's singles, and all four will play what could be the deciding match in mixed doubles to follow.
Australia, led by Lleyton Hewitt, plays Spain in the only match Sunday.
On Monday, Wimbledon champion Kvitova and Tomas Berdych play for the top-seeded Czechs against Bulgaria, and the United States - Bethanie Mattek-Sands and Mardy Fish - take on world women's No. 1 Caroline Wozniacki and Frederik Nielsen of Denmark.