Stosur was drawn against Germany’s second-ranked player and world No.
28 on Friday for the tie, which will be contested on the hard-courts of Pat Rafter Arena.
Casey Dellacqua will battle Germany No.1 Angelique Kerber in the second match on Saturday, while the reverse singles will be played on Sunday, followed by doubles.
Ash Barty and Casey Dellacqua, who reached three grand slam doubles finals last year, will play doubles for Australia.
Forty years have passed since Australia last tasted Fed Cup title success when Evonne Goolagong led the way.
And it has been more than two decades since they even featured in a final, but Australian captain Alicia Molik believes history will be on their side.
On paper the hosts are the underdogs against a German outfit boasting world No.7 Angelique Kerber and former top 10 player Andrea Petkovic.
However, Molik gave a not so subtle reminder that her team emerged triumphant in their last Fed Cup clash in Stuttgart two years ago.
And Molik believed Sam Stosur was still the trump card that would help provide a psychological edge despite the former US Open champion slipping to world No.19.
“I think we can win,” Molik said.
“It will be very clear in the Germans’ minds that Sam had the edge (last time in Stuttgart).
“As an opponent it is always difficult going into a match knowing that you lost the last encounter.
“I am hoping they (Germany) remember those matches very clearly.”
Former world No.4 Stosur has only made it past the third round at one tournament this year and has struggled in the past with public expectation on Australian courts.
But Stosur has clearly bought into Molik’s approach that Germany were the ones under the pump in Brisbane despite waiting decades for another crack at a Fed Cup title.
“I don’t think that is going to be a crucial factor, it’s not going to make us any more nervous or feel more pressure,” said Stosur when reminded their last semi-final and final was way back in 1993.
“Obviously we would like to break that drought.
“But we are going to go out there and play as if we were in the final last year.”
As world No.53 Dellacqua will take on a player ranked 46 places higher in the opening singles.
But the busy Dellacqua is no weak link after claiming three wins over top-20 players this year alone.
“Casey would be leading the charge from both teams in the amount of matches she has been able to put together – you can’t buy that match time,” Molik said.
The Czech Republic and Italy are playing in the other semi-final this weekend. The winners meet on November 8-9 in the final.