Williams, who coached Port Adelaide to the AFL flag in 2004, has spent the past five seasons at Melbourne as the Demons' head of development.
The 67-year-old, who played 286 games across stints with Collingwood and Brisbane during a decorated VFL/AFL career, will head up Hawthorn's AFLW development program.
Hawthorn finished fourth on the AFLW ladder last year with an impressive 9-3 record, before being knocked out of the finals in straight sets.
"We are thrilled to add a person of Mark's calibre to our football club, he will benefit our program immensely," Hawthorn's AFLW general manager Keegan Brooksby said in a statement on Thursday.
"With almost five decades in football, Mark's experience speaks for itself.
"He is an expert at building relationships and cultivating environments where players thrive."
Williams coached Port Adelaide for 12 seasons before leaving at the end of 2010.
He took up assistant and development roles at Greater Western Sydney and Richmond, before playing an important off-field role at Melbourne, which included the club's 2021 flag.
Williams' extraordinary service to the game was recognised in 2023 when he was inducted into the Australian Football Hall of Fame.
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