Australia number one Tomic and world number 33 Kyrgios, who won his maiden ATP title at the Marseille Open on Sunday, will lead off the singles on the temporary grass court at Kooyong Lawn Tennis Club.
Peers, ranked ninth in the world in doubles, will team up with big-serving Sam Groth in the doubles rubber, team captain Lleyton Hewitt said in Melbourne on Tuesday.
Peers reached two grand slam finals last year with Andy Murray's older brother Jamie Murray and had earned his spot, twice grand slam champion Hewitt told reporters.
"I spoke to him at the Masters Cup in London at the end of last year and we talked about what he wanted to do with Davis Cup and the Olympics and he put his hand up for an opportunity," said Hewitt, who retired from tennis after the Australian Open.
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Hewitt lavished praise on 20-year-old Kyrgios, who defeated world number seven Tomas Berdych and former U.S. Open champion Marin Cilic on his way to winning in Marseille.
"We all knew he was going to win a title, it was a matter of time but the way he did it and the guys he beat, especially from the quarter-finals on was very impressive," Hewitt said.
(Reporting by Ian Ransom; Editing by Amlan Chakraborty)
