Miller, now 32 and plying his trade for Brisbane Roar, made 22 appearances for United between 2004 and 2006.
The Irishman is one of 20 players who have been selected in the All-Stars squad following a process that included votes cast by fans, coaches and influential figures within the Australian game.
Juventus legend Alessandro Del Piero was part of the initial 35-man squad (he plays for Sydney FC), but won't figure in the match as he's enjoying a summer break in Italy.
Japan international Shinji Ono is similarly unavailable but former Blackburn Rovers midfielder Brett Emerton will pull on the All-Stars jersey alongside Miller. Defender Michael Beauchamp has also previously played against the Reds; he featured for Aalborg in the Champions League back in 2008/09.
All-Stars coach Ange Postecoglou is confident Saturday's match will be a memorable occasion for football fans in Australia and is relishing the chance to pit his managerial wits against David Moyes.
"It's an opportunity to measure yourself against the best," he said. "It's got all the things I look for in my job. It's a challenge and I love that. I coach best when it's like that, I get more excited."
All Stars: Goalkeepers Covic, Theo Defenders Bojic, Grant, Boogaard, Chapman, Risdon, Beauchamp, Topor-Stanley, Rose Midfielders Miller, Emerton, Broich, Celeski, McGlinchey, Carrusca Forwards Bridge, Berisha, Williams, Ifill