In what will be his first Australian coaching gig in seven years, Montemurro will take the reins of the All Stars for their clash against the Women's Super League (WSL) side at Marvel Stadium in Melbourne on May 24.
Announced on Friday, Montemurro's appointment comes in the wake of his release by Juventus last month after almost three years with the Italian soccer juggernauts.
The 54-year-old threw his hat in the ring to become the Matildas coach before moving to Juventus in 2021, and is a strong contender should current boss Tony Gustavsson move on.
In the wake of Australia's strong showing in the 2023 World Cup, Gustavsson was strongly linked with the top job with the US women's team, subsequently filled by current Chelsea boss Emma Hayes, and has also been a target for his native Sweden.
He is currently contracted until the end of the Paris 2024 Olympics, with Football Australia saying when speculation surfaced in November that discussions over his future would be held at "an appropriate time".
Montemurro will be assisted with the All Stars by Central Coast Mariners coach Emily Husband - who has led her club to the semi-finals in their first season back in the competition - and Western United boss Kat Smith, who achieved a third-place regular-season finish in the ALW.
Melbourne Victory's Melissa Maizels has been appointed goalkeeper coach for the All Stars.
"I wish to thank the A-Leagues team for including me as part of this historic event," Montemurro said on Friday.
"I look forward to reconnecting with the Australian football public and working with Kat, Emily and Melissa - showcasing the exciting talent of the A-Leagues."
Born and raised in Melbourne, Montemurro was snapped up by Arsenal in 2017 after leading Melbourne City to a premiership and back-to-back championships - in the process becoming the first coach to go through a full season undefeated.
In his four years with Arsenal, Montemurro took out the league and the WSL Cup, and was nominated for coach of the year awards by world governing body FIFA and their European equivalent UEFA.
The Australian's winning ways continued when he joined Juventus.
In his first season, he led the side to a first-ever treble of the Serie A Femminile, the Coppa Italia and the Supercoppa Italiana.
He would go on to add a second Coppa Italia triumph in 2022-23 and another Supercoppa Italiana trophy in 2023-24 before parting ways with the club in March.
