Two goals in three minutes from summer signings Sarah Mayling and Remi Allen turned the game around after Natasha Flint had put the Foxes ahead in the first half.
Despite the introduction of Lachante Paul and Charlie Devlin, Leicester couldn't find the equalising goal and their debut season in the top flight ends in defeat.
Story of the match
In her first fixture in charge at Villa, Carla Ward handed seven summer signings their debut, with Allen captaining the side against her former employers.
Goalkeeper Hannah Hampton started in goal whilst three of the back four made their debut including the return of Mayling.
Swiss international Alisha Lehmann and Chantelle Boye-Hlorkah joined Jodie Hutton as the home sides front three.
For the Foxes, in their first-ever Super League fixture, Jonathan Morgan started four of his seven recruits.
Former Manchester United players Abbie McManus and Jessica Sigsworth made their debut alongside Georgia Brougham and Molly Pike.
In a cagey opening 10 minutes, it was the Foxes who managed to find space behind on two separate occasions. The first one nearly saw summer signing Sigsworth, but Sargeant recovered to deny the striker.
A few moments later and Flint came close. She twisted and turned outside the area only for Hampton to brilliantly tip the ball over for a corner.
Sigsworth did manage to test Hampton after 15 minutes from the edge of the area. Hannah Cain did terrifically well to keep the ball in play on the left before the ball eventually found the former United striker, whose shot was straight at the goalkeeper.
Moments later and Morgan's side should have taken the lead. A well-worked corner saw Cain whip the ball into the box perfectly to the unmarked Sam Tierney, but the defender headed wide from point-blank range.
Leicester's pressure continued and were denied again when Hampton pulled off a sensational save after half-hour to deny Flint from 25 yards out. Cain's corner was headed to the edge of the area to the 25-year-old, whose thunderous strike was denied by the diving goalkeeper.
But despite her heroics to deny Flint, Hampton was unable to deny the striker's powerful left-footed strike as the ball was palmed into the net.
Shannon O'Brien picked the striker out on the edge of the area and the striker opened her account for the season with the help of the goalkeeper.
Both sides made changes at half-time. The hosts introduced Shania Hayles in place of Hutton and switched Boye-Hlorkah onto the right-hand side.
The Foxes started the second half in the same vein as they finished the first half and Sigsworth should have opened her Foxes tally. The ball was threaded through and the striker shrugged off Anita Asante before seeing her effort saved by Hampton's foot.
Out of nowhere and the game has turned on its head. Villa levelled the scoring from a quality free-kick from Mayling placed the ball with conviction pass Kirstie Levell.
Immediately after kick-off and Leicester handed Villa the chance to go ahead. A mix-up at the back saw Lehmann bear down on goal before cutting the ball back for Allen to bundle the ball into the back of net.
Morgan threw Devlin and Paul onto the pitch in search of a leveller, but the away side struggled to create a key chance.
They did comer close, when Brougham's cross was nearly put away by Sigsworth, but the striker missed the target.