It will be the first time in a decade of cricket at the highest level that Moloney has been based outside her native Tasmania.
The 29-year-old off-spinner has been a mainstay of the Hobart Hurricanes since the inception of the WBBL, having played 74 games across seven seasons, a testament to her longevity.
She will bring a wealth of experience to the Stars as well as her leadership skills, having previously led the Hurricanes as captain in WBBL|04. Moloney played every game in WBBL|07 providing valuable off spin as well as lower order runs.
Moloney said she's looking forward to challenge of a new environment:
"I'm really looking forward to spending WBBL|08 with the Stars. To play with the likes of Meg Lanning and Annabel Sutherland is a fantastic opportunity and one I couldn't pass up.
"I've loved my time at the Hurricanes but hopefully I can hit the ground running for the Stars and make an immediate impact with both bat and ball.
"I can't wait to get started and meet all my new teammates as well as the passionate Stars members and fans."
Melbourne Stars General Manager Blair Crouch said:
"We're rapt to welcome Sasha to the Stars family for WBBL|08. She has been a constant figure for the Hurricanes over her entire career so far and we hope that she can share her leadership and experience with the Stars, especially our young and developing talent among the squad.
"There's no better place to play cricket than in Melbourne and we can't wait for Sasha to experience that on a regular basis.
"We look forward to announcing the rest of our squad in the coming weeks plus the fixture release, where our fans will get to support the Stars in Victoria for the first time since 2019."