The seven-time champions have not tasted success in the tournament since the days of Evonne Goolagong in 1974, with two-time winners France standing in their way on the hardcourts at Perth Arena starting Saturday.
It will mark the last Fed Cup final played under the current format, with an overhaul next year seeing 12 nations compete in a six-day event in Budapest.
While there will be a huge boost in prize money, it spells an end to home ties, following a similar change to the men's Davis Cup.
Barty, fresh from being crowned WTA Finals champion in Shenzhen on Sunday, leads a team that boasts world number 51 Ajla Tomljanovic making her debut, veteran Samantha Stosur (96), Astra Sharma (108) and Priscilla Hon (126). They are banking on passionate home support to get them over the line.
"This was a week I circled at the beginning of the year that I wanted to target, and to be able to finish the year playing as a team for your nation is pretty special and I've been looking forward to it for a long time," said Barty. "All of us are extremely hungry — it's taken us probably two or three years to get into this position and now it's about coming out and enjoying it this weekend."
France captain Julien Benneteau has kept faith with the team who sealed their semi-final win over Romania, led by Kristina Mladenovic, ranked 40 in the world.
She will be backed by 45th-ranked Caroline Garcia, Alize Cornet (60), Fiona Ferro (63) and Pauline Parmentier (122) as they target a first title since 2003.
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