Husband departed the Mariners on Monday, after two incredibly successful years at the helm, to take up a full-time role with Football Australia.
The Englishwoman was A-League Women (ALW) coach of the year in her first season in 2023-24 when she built the Mariners' squad from scratch, then led them to the semi-finals.
She backed up by claiming the club's first ALW championship this year.
Husband reunites with Montemurro as his first backroom appointment after serving as his assistant for last year's ALW All Stars game against Arsenal.
"Emily is an astute, modern coach who's already proven her quality at the domestic level," Montemurro said.
"Her work with the Central Coast Mariners has been phenomenal and demonstrates the qualities she will bring to the Matildas.
"Emily has a deep understanding of the game, an ability to connect with players, and a fresh perspective that will be invaluable to our set-up. I'm looking forward to working closely with her once again."
Husband was involved in Tom Sermanni's last camp against Argentina as part of FA's 'Team of Coaches' development initiative.
The former Canberra United assistant will start ahead of Montemurro's first games against Slovenia on June 26 and 29, then Panama on July 5 and 8, in Perth.
It is the latest step in Husband's incredible rise from a backpacker who became a coaching force at Sydney University while on a working holiday visa, to one of Australia's top-rated mentors.
"To be trusted with the chance to contribute, even in a small way, to the Matildas and their future is an absolute privilege," Husband said.
"Joe is someone I've always had enormous respect for. Not just for his football brain, but for the way he leads.
"We've had the chance to work together before, and I'm genuinely thrilled to build on that now as we hopefully play a part in guiding the Matildas to reach greater heights."
Husband's appointment also helps address a dearth of women in senior coaching roles at FA, following the departure of Melissa Andreatta (Scotland women's national team head coach) and Leah Blayney (Japan women's team assistant).
"We're thrilled to welcome Emily Husband to the Matildas coaching team," head of national teams Gary Moretti said.
"Emily is one of the most exciting coaches in Australian football and we're proud to see her progress into the national team environment."
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