Despite winning the 2011 US Open and making the French Open semi-finals four times, Stosur has long struggled to deal with the limelight in Australia.
Australia are seeking their first Fed Cup since 1974, while France last won in 2003.
Should she win 2 singles matches, she will become the 10th player to complete a flawless year in Fed Cup singles since 1995. Ending a 45-year drought would be a dream ending of Barty's 2019 campaign.
"This was a week that I earmarked earlier in the year", Barty told media. "So it's someone I would love to play and try and right my wrongs from midway through the year when we played in Rome".More news: Liverpool or Man City?
Barty will play Mladenovic in the first reverse singles on Sunday, followed by Tomljanovic taking on Garcia, although late changes can be made by the team captains.
Dropped from the second singles slot for the final, with world No. 51 Ajla Tomljanovic taking her position, Stosur will wait to see if this weekend's tie is forced to the doubles match in order to make an appearance.
They last claimed the title in 1974 during a golden era for Australian tennis when former world number one Evonne Goolagong was in her pomp. But despite the titles and wins coming her way, the 23-year-old was quick to brush off any accolades.
In contrast, Tomljanovic has had a good year and spent most of it inside the world's top 50.
"Saturday's going to be probably the highlight of my year and my career so far", she said.More news: Saudi Aramco Stock Offering to Launch November 17
"When you play a Fed Cup final with the number one in the world on the other side, and away, you can not say that you have an advantage", he said on Wednesday.
Now unbeaten with a 6-0 record for rubbers this year, she became the first player to contest and win the maximum number of matches on the way to the Fed Cup Final in the competition's current format, having claimed clean sweeps during Australia's victories against U.S. and Belarus earlier this year. "Sam has paved the path for all of us, we've all grown up watching her, we've had the privilege of playing with her, playing against her, and I think I'm just trying to do my best to run off that". They are banking on passionate home support to get them over the line.
"It was an experience and it's a positive", she said.
Australia has performed France 6 occasions in Fed Cup historic previous and has a 5-one edge, however misplaced when the groups final performed in France in 2000.More news: Father Of Atatiana Jefferson Dies After Suffering Heart Attack
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