A French Open quarter-finalist this month, the world No.9 was on Wednesday named among a nine-strong Australian contingent to compete in Paris from July 27.
De Minaur will play both singles and doubles, his Olympic debut three years in the making after the 25-year-old was ruled out on the eve of the Tokyo Games when he contracted COVID-19.
Current doubles world No.1 Matt Ebden (doubles), Alexei Popyrin (singles), Chris O'Connell (singles) and Rinky Hijikata (singles) will also debut, while fit-again Ajla Tomljanovic (singles), Ellen Perez (doubles) and Daria Saville (doubles) will play at their second Olympics.
Doubles specialist John Peers will partner Ebden in his third Olympics, the pair hoping to replicate Todd Woodbridge and Mark Woodforde's run to gold in 1996 that remains the country's only Games tennis title.
Triple Olympian Lleyton Hewitt will captain the men's team, while Australia's only five-time tennis Olympian Sam Stosur will lead the women's team in Paris.
Jordan Thompson, Australia's clear No.2 in singles at No.39 in the world, chose to skip the Games and instead defend rankings points on the ATP Tour.
Max Purcell, who played singles for Australia at the Tokyo Games, could have taken a doubles spot but has also opted out as he tries to improve his singles ranking of No.94.
The French Open venue will be just the second Olympic event on clay and first since Barcelona's 1992 Games.
"I have always wanted to be an Olympian," de Minaur said ahead of his Wimbledon campaign from Monday.
"Last time round I got a little bit unlucky to not be able to play in Tokyo, but I've had my eyes set on Paris and I am super excited to now be officially part of this team.
"I am really looking forward to just immersing myself in what it means to be an Olympian.
"I am excited see all the other sports, meeting some of my fellow athletes and teammates and making some new Aussie friends."
Ajla Tomljanovic made it to the final of the grass-court tournament in Birmingham. (AP PHOTO)
Tomljanovic signalled her recent run of injury may be behind her when she beat four top-60 opponents on the way to a first tour-level singles final in more than five years, on grass in Birmingham last week.
"I am feeling good ... every match I have under my belt brings me closer to the level of play I want to get to," the former world No.32 said.
"Physically I am pulling up well after matches, which is the most important thing, so I am very happy with my health, and I think the more time I get on court the better I will be for Paris."
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