The trio, who have 62 grand slam titles between them, will be joined by Naomi Osaka, Caroline Wozniacki, Nick Kyrgios and Stefanos Tsitsipas, it was confirmed on Wednesday.
Scheduled to take place on January 15 at Melbourne Park's Rod Laver Arena, the Australian Open Rally for Relief will donate proceeds from ticket sales -- priced at $37 (54 AUSD) for adults and $24 (35 AUSD) for concessions -- to the bushfire relief efforts.
At least 24 people have been killed by the fires in Australia. Nearly 18 million acres of land have been burned as the country faces its worst blazes in decades.
"This unprecedented bushfire crisis is devastating people, properties, communities, livestock and animals across the country and our hearts go out to all those affected," said Tennis Australia CEO Craig Tiley in a statement.
"The response from the tennis community -- our players, clubs, partners and international tennis bodies -- has been overwhelming and it's wonderful to see everyone pull together.
"The players are keen to be involved -- we've had a tremendous response from them and they are keen to help."
Kyrgios kick-started tennis' fundraising efforts last week when he pledged $140 (200 AUSD) for every ace he hits at upcoming tournaments with a number of other players since joining him.
Tennis Australia will also donate $69 (100 AUSD) for every ace hit across six tournaments, including the Australian Open, as well as granting $700,000 (1 million AUSD) to help rebuild tennis facilities damaged in the bushfires.
The Women's Tennis Association (WTA) is matching Tennis Australia's $69 donation for every ace hit at the Brisbane International, Auckland's ASB Classic, the Adelaide International and the Hobart International.
Maria Sharapova, who has been granted wildcard entry for the Australian Open, has donated $17,400, with world No. 2 Novak Djokovic agreeing to match her.
Sharapova also announced on Wednesday that she had left 10 signed pairs of her tennis shoes in her Brisbane hotel that members of the public could buy with a $206 (300 AUSD) donation to the Australian Red Cross.
It's not only tennis stars who have pitched in with their support.
Australian cricket legend Shane Warne has auctioned the baggy green cap he wore throughout his test career, which has so far reached $343,000 (500,000 AUSD).
Several one-day batsmen, including Glenn Maxwell, Chris Lynn and D'Arcy Short, are donating $250 (175 USD) for every six they hit at this year's Big Bash League, the country's professional Twenty20 competition.
Alongside support from the league, nine Australian NBA players have agreed to contribute $750,000 towards recovery efforts.
"We are heartbroken over the devastation these fires are causing all across our homeland," the players, which include Philadephia 76ers' Ben Simmons and San Antonio Spurs' Patty Mills, said in a joint statement.
"Our thoughts are with our families, friends and all of the people of Australia. We hope you feel our love and support and know that we will continue to bring awareness to this crisis globally and provide assistance in any way we can."
Australian Open organizers have said that the tournament, scheduled to begin on January 20, will likely go ahead as planned despite initial fears that smoke blown over Melbourne from the fires could delay the start.