The in-form Gibson and Birrell, who both secured breakthrough career-high rankings last month, are joined by two-time WTA champion Maya Joint, and the experienced former world No.1 doubles player Storm Hunter.
Australia are playing France for the first time since suffering a heartbreaking 3-2 loss in the 2019 final as Ash Barty and Ajla Tomljanovic went painfully close to leading the country to a first title in 45 years.
The showdown will also be the first time in the prestigious team event's 63-year history where the nations meet on French soil - at Le Chaudron in Le Portel.
The winners of the November 21-22 clash will progress to next year's Cup qualifiers and move one step closer to securing a place in the 2027 finals.
The losing nation will battle it out in a 2027 regional group with an aim to progress back into the qualifiers and finals in 2028.
Australia team captain Samantha Stosur believes she has picked a formidable line-up, with one more player to be added next month.
"It's fantastic having two players in the top 50," Stosur said.
"It's exciting for Australian tennis overall and obviously those two (Birrell and Gibson) individually. Success breeds success and more than anything, it pushes everyone else to try and get to that spot."
Gibson had an amazing run through March on the US hard courts and recently made her first WTA final in Singapore, while Birrell won her maiden WTA title in Seoul last month.
Australia's 2019 heartbreak will provide some extra motivation for Stosur, who also played in that tie.
"I might bring that up," said the former US Open champion.
"This is the first time playing them since then and I'll be gunning for the win, that's for sure."
The nations will compete in a best-of-five-rubber format, consisting of four singles matches and one doubles match, and each match played as best-of-three sets.
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