Villani, who is preparing for Australia's Ashes tour to England, will move out from Perth Scorchers where she featured in 58 matches and scored 1706 runs in four seasons.
"It's exciting to come home to Melbourne for the WBBL. I feel as though the Stars is a good fit for me as I really like the culture they have developed. I can't wait to join up with the entire squad come the start of the season," Villani said in a statement.
"I am eager to see where this team can go, both on the field and how we can continue to build on a strong culture off the field. I'd really like to thank the Perth Scorchers for the past four seasons and am now looking forward to the next stage of my career," she added.
"Elyse is a world-class cricketer and we are very happy to gain her signature. I'm sure she'll come in and have an immediate impact. We're looking forward to seeing what Elyse will bring to the team, not only on the field but the influence she'll have on the younger players in helping them to develop their games," Hemp said.
The standalone fifth season of WBBL will commence under lights at North Sydney Oval on October 18 and end with the Grand Final on December 8. Melbourne Stars will open their campaign against Hobart Hurricanes on October 19 at Junction Oval.
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