Spurs took the lead through star signing Bethany England on her debut, but Villa had come from behind just 10 minutes later.
Kenza Dali equalised with a 20-yard strike before Rachel Daly turned home a Kirsty Hanson cross.
This match was the first for 31 days in the WSL, with Spurs losing the final game of 2022 and the first of 2023.
Defeat leaves Spurs in eighth with nine points from 10 games, while Villa rise to sixth having won five and lost five of their matches.
Number nine for hot-shot Daly
Lionesses dominated the build-up with England’s reported £250,000 switch to Spurs from Chelsea, which would be a record fee for a transfer between WSL clubs. There was also plenty of focus on Lucy Staniforth and Jordan Nobbs, who started in midfield for Villa following moves from Manchester United and Arsenal respectively.
However, it was Daly who proved decisive as she scored her ninth WSL goal of the season to move clear at the top of the scoring charts, ahead of Manchester City’s Khadija Shaw.
It continues Daly’s push to start up front for England, having played at left-back so far under Sarina Wiegman, including every game of the Euros triumph last summer.
Her goals have now been worth 10 points to her club, and her nine goals also account for 60% of the 15 they have scored in the league so far this season.
England might be worth £250,000, but Daly is priceless for Villa manager Carla Ward and her team.
Five in a row for sorry Spurs
England put Tottenham ahead in rainy and blustery conditions at Bescot Stadium, the first goal Spurs have scored in five WSL games.
The England striker swept home a Chioma Ubogagu cross from six yards after 28 minutes, to show quality she was unable to demonstrate from the Chelsea bench.
However, she could not stop the rot as Spurs slid to a fifth successive league defeat, proving the problems run far deeper for Rehanne Skinner’s side.
England’s strike was the only time they ventured into the Villa box with real purpose in the first half, and after the break they failed to offer any greater threat until the 89th minute, when England skewed over from 12 yards when she should have found the target.
They have issues in goal – Tinja-Riikka Korpela replaced Becky Spencer, who conceded three to Everton in the final WSL game of 2022, but she was culpable for Dali’s first as she misjudged the shot from the edge of the D.
Spurs also lack creativity without Ashleigh Neville, absent here after being sent off against Everton. No defender has scored more (three) or been involved in more goals (five) in the WSL this season than Neville.
Villa rise into the top half with this win, while Spurs are now entrenched in the bottom six. Skinner must turn things around quickly to save their season, starting against rock bottom Leicester City next up.