Villani top-scored with 58 at Melbourne's Citipower Centre (Junction Oval) as the Scorchers chased down their target of 144 with three balls to spare on Saturday.
Perth's imposing top order also features fellow T20 World Cup winners Meg Lanning and Nicole Bolton, but Lanning faced just 12 balls before Brooke Hepburn had her caught behind on eight.
Bolton (4) and Heather Graham (7) also didn't produce the innings they would've liked, but Villani steadied the ship before her superb knock came to an end on 58.
Experienced campaigner Lauren Ebsary (40 not out) and Chloe Piparo (26 not out) steered the Scorchers home with a fifth-wicket partnership that highlighted the team's impressive batting depth.
"I think we've got an extremely deep batting order," Villani said.
"It just means that we've all got the ability to play with freedom, knowing that at some point everyone's games are going to come off ... if we each commit to playing that style of cricket, it's going to be to the benefit of the team."
The Hurricanes managed to put up a solid fight despite lining up without any of their imports, after 20-year-old opener Erin Fazackerley (38 off 16) got the Hurricanes off to a good start.
Perth managed to bring the run rate down during the middle overs, with Heather Graham (3-25) the pick of the bowlers.
The Scorchers head to Sydney on Wednesday for two matches, a grand final rematch against the Sixers on Friday before taking on Brisbane on Saturday.