World No 5 Alexander Zverev will face rookie Alex de Minaur first up in Germany's Davis Cup tie against Australia on Friday, with Jan-Lennard Struff opening against Nick Kyrgios.
De Minaur, 18, was rewarded with a place in the Australian team after making the semi-finals at the Brisbane International last month and the final in Sydney before going out in the first round of the Australian Open.
Team captain Lleyton Hewitt confirmed De Minaur would make his debut against Germany's Zverev in the opening singles match at Pat Rafter Arena in Brisbane.
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"The calibre of player he has beaten this summer has been pretty impressive," Hewitt said of De Minaur. "He's obviously got a big task in the first match but he's got nothing to lose."
The dangerous Zverev reached the third round of the opening grand slam of the year last month before falling to South Korea's Chung Hyeon.
The maturing Kyrgios - Australia's No 1 - then faces Struff, who was knocked out of the Australian Open by eventual champion Roger Federer.
Hewitt resisted the urge to play himself in the doubles despite training with the team this week after his run to the quarter-finals at Melbourne Park with Sam Groth.
He opted for Matthew Ebden to partner doubles specialist John Peers against Germany's Peter Gojowczyk and Tim Puetz on Saturday before Sunday's reverse singles rubbers.
Hewitt, 36, said that he was never seriously considering playing in Brisbane.
"It's not happening," he said.
The doubles and reverse singles match-ups of the first round tie can be changed up to an hour before the players take the court on Saturday and Sunday.
