Montemurro officially kicked off his tenure on Monday and on Tuesday announced sweeping changes to his technical and support staff, with four appointments and several departures.
Later this week, he will announce an extended squad for his first games at the helm against Slovenia and Panama in Perth.
Former Central Coast Mariners coach Emily Husband was appointed as an assistant last week and Joe Palatsides, who served as Montemurro's assistant at Lyon, will join her.
Highly-rated development coach Palatsides is best known for his work with the academies at Melbourne City and Melbourne Victory, developing talented young players for their respective A-League Men teams.
Former England international goalkeeper Leanne Hall, who previously held coaching roles with Arsenal and Aston Villa's women's teams, joins as set piece coach.
Montemurro has also brought along physical performance coach Emanuele Chiappero, who he worked with at Juventus and Lyon.
James Slaveski, who is the under-18s academy coach at Sydney FC and has held analyst roles there and at Victory and City, joins as video analyst.
"Each of our new staff members bring specific expertise that will complement our current group and elevate the holistic preparation of our players," Montemurro said in a statement.
"The international game continues to evolve rapidly, and we are committed to staying at the forefront of coaching, analysis, and performance.
"I look forward to working closely with Emily, Joe, Leanne, Emanuele and James as we continue to build for an exciting cycle of tournaments."
Analyst Marty Judge and sports scientist Tim Knight are among the long-serving staff members to move on.
The Matildas play Slovenia at HBF Park on June 26 and 29 then Panama at Bunbury's Hands Oval on July 5 and HBF Park three days later.
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