He began coaching in youth football for various Victorian clubs, before his first managerial role with Sunshine George Cross, and then later, Coburg United.

Montemurro spent his entire junior playing career at Brunswick Juventus and made his first senior appearance for the club in 1986 in the National Soccer League as a 16-year-old.

[citation needed] His first major role was as youth coach (U21) in the Victorian Premier league with Green Gully in which he took the team to the runner-up position in his first year.

[citation needed] He opted to continue his youth coaching at cross town rivals South Melbourne in which he guided the team to the runner-up position in 2005.

[citation needed] In 2010, he returned to South Melbourne as a youth coach and guided the team to a historic undefeated season as champions.

[citation needed] Montemurro was appointed head coach of the Melbourne Victory FC W-League on 16 May 2014 and guided it to the runner-up position after the home and away fixture, the highest finish in the club's history.

[16] In June 2016, Montemurro's role at City was expanded to include assisting John van 't Schip with the senior men's team.

[18] In November 2017, Montemurro left Melbourne City to join Arsenal Women as manager, after Pedro Martínez Losa was sacked following a poor start to the season.

[19][20][21] On 14 March 2018, he won his first major trophy with Arsenal by beating Manchester City 1–0 to win the FA Women's League Cup.

[22] On 15 May 2018, he led Arsenal to the Women's FA Cup final in front of a record attendance of 45,423 at Wembley Stadium, in which they lost 3–1 to Chelsea.

[citation needed] On 7 February 2019, the team reached its second consecutive Continental Cup League final, beating Manchester United 2–1 at Meadow Park.

[citation needed] The team was also part of a record-breaking WSL attendance, when 38,200 spectators came to watch the first ever North London Derby at Tottenham Stadium; Arsenal won the match 2–0.

[33] Despite retaining the support of the Arsenal board, Montemurro decided to leave the club in order to take a break and spend more time with his family.

[citation needed] He is of Italian descent as his family moved from southern Italy to settle in Australia, following the end of World War II.

[citation needed] The 1979 FA Cup Final, in which Arsenal beat Manchester United 3–2, served as an inspiration for Montemurro to pursue a career in football.