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).
Picking Tomljanovic was a bold move by Molik as Australia bid for a first title in 45 years, with Stosur her country's most successful ever singles player, spanning 16 years of Fed Cup action.
Those four players are scheduled to be part of the reverse singles on Sunday, although that can change, before a potentially decisive doubles clash, where the massively experienced Stosur is set to partner Barty against Garcia and Mladenovic.
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.More news: Amazon's pre-Black Friday sale is here: Shop the best deals
"Fed Cup is in my calendar before any other tournament", Barty said. The closing is changing into performed on tough outside courts at Perth Enviornment.
In contrast, Tomljanovic has had a good year and spent most of it inside the world's top 50.
"I know that I've got Mol [Alicia Molik] sitting on the court next to me in such a supportive and incredible captain and I think that knowing that all of our team is sitting on the side of the court it just brings out this little bit of a different side to me and it's pretty rare and it doesn't happen often". "Kiki has the ability to play well in the big moments", Barty said.
"For us it was a matter of match-ups and I feel like we are going in with our strongest two players for Saturday", said Molik.More news: Secretary of State Pompeo's role examined in impeachment inquiry
Each equally Barty, who gained final weekend's WTA Finals in China, and Stosur and Mladenovic/Garcia acquired a few-established dwell fifth doubles matches in April's semifinals to ship their global locations to the last word.
Barty is the first world number one to feature in a Fed Cup Final since Martina Hingis in 1998 and will look to extend an unbeaten streak of 14 matches in the competition.
"It was an experience and it's a positive", she said. Should she win 3 matches this weekend - as she did in both the World Group first round and semifinals this year - she will become the first player to win the maximum possible number of Fed Cup matches in a year (9) since the current format was adopted in 1995.
The Australian's last defeat in the Fed Cup came back in 2017.More news: Brazilian judge orders release of ex-president
"That final was a great lesson for me and all of us", said Garcia, who won two singles matches in the tie.