World No.52 Bernard Tomic will partner 2011 US Open winner Sam Stosur in Australia’s Hopman Cup campaign this summer.
And world No.4 Agnieszka Radwanska will join forces with Wimbledon semi-finalist Jerzy Janowicz in Poland’s debut at the mixed teams event.
Event organisers are still on the lookout for a new partner for France’s Jo-Wilfried Tsonga following the shock retirement of Wimbledon champion Marion Bartoli.
Five more teams will be announced over the coming month.
Tomic beat world No.1 Novak Djokovic at last year’s Hopman Cup, and went on to make the third round of the Australian Open before losing to Roger Federer.
The 20-year-old also reached the four round of Wimbledon.
Australia haven’t won the Hopman Cup since Mark Philippoussis and Jelena Dokic went all the way in 1999.
The tournament will be held at the Perth Arena from December 28-January 4.