Dallacqua and Stosur are likely to face a strong doubles pair in the USA's Bethanie Mattek-Sands and Coco Vandeweghe.
Mattek-Sands, ranked no.3 in world doubles, has never lost a doubles match in the Fed Cup. She and Vandeweghe not only won their first doubles match together in USA's February win over Poland but also the Indian Wells doubles title last month.
But Dellacqua says the experience she and Stosur possess will stand them in good stead.
"Obviously, they're a quality team, they've played one tournament and won a big event so - and obviously, Bethanie's credentials on a doubles court, we all know what they are," Dellacqua said.
"But that's not to say both myself and Sam, who's been No.1 in the world of doubles before ... I don't care what you say - when you go No.1 in world doubles, you're a pretty good doubles player too.=," she said.
"I think we can take confidence in the fact that, in Slovakia just recently, we won the live deciding rubber. We've also been playing together and played some really tough matches recently."
Stosur and Russian-born Daria Gavrilova are set to play in Australia's singles rubbers. First up, Gavrilova will face Madison Keys and Stosur Christina McHale.
The winning team will re-enter the eight-nation World Group I for 2017, with the losing nation relegated to World Group II.