Australian captain Sam Stosur on Tuesday named Gadecki alongside stalwarts Daria Saville and Ajla Tomljanovic and doubles specialist Ellen Perez for the November 13-20 finals in Malaga.
Gadecki is riding a wave of confidence after rocketing up 64 places in the rankings to No.88 in the world following a stunning run from qualifying to the final in Guadalajara, Mexico last week.
The 22-year-old claimed four top-100 scalps, including those of second-seeded former Australian Open finalist Danielle Collins and 2017 US Open champion Sloane Stephens.
"Being in the top 100 has been a massive goal of mine and to reach it after a strong run this week is incredible," Gadecki said.
"I'm looking forward to being back playing solid tennis and leaving it all out on the court.
"It means so much to be selected to represent Australia again.
"I'm looking forward to spending time with the girls and being out there as a team.
"I think we can really do some damage."
Australia reached the Cup final in both 2019 and 2022 and Stosur believes she has a team capable of challenging once again for the trophy.
"We know what it takes, and we want to get back there and push for that next step," Stosur said.
"Our team has a solid mix of experience and emerging talent.
"Olivia making her top-100 debut and Ellen as world No.10 in doubles puts us in great stead.
"We're ready to play our best tennis and do Australia proud."
Officials have tinkered with the format for this year's event, with the round-robin group stage replaced with a knockout competition.
Eight teams will begin in round one, with the four seeded teams - Australia, Canada, Italy and Czech Republic - receiving byes into the quarter-finals.
Australia will face the winners of the Slovakia v USA tie on November 17 before semi-finals take place on November 18-19.
The final will be played on November 20.
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