Nigel Pearson's side held the lead for all of four minutes at Villa Park before succumbing to goals from Ciaran Clark and Alan Hutton, while Paul Konchesky was sent off
The Foxes took the lead through Leonardo Ulloa's tap-in in the 13th minute but that advantage lasted only four minutes, Ciaran Clark heading in from Ashley Westwood's free kick to restore parity.
After some great saves from both goalkeepers, though, Villa seized the lead through an unlikely source when Alan Hutton made an untracked run from right-back before keeping his composure to take a touch and fire past Brad Guzan.
To make matters worse, Leicester full-back Paul Konchesky was controversially sent off for a challenge on Hutton with 10 minutes to go.
The home side started on the front foot but it was the visitors who opened the scoring in the 13th minute. Riyad Mahrez jinked his way in from the right flank and his tame shot, which took a slight deflection off Clark, should have been held by Guzan but the goalkeeper spilled the ball into the path of Ulloa, who tapped home the rebound to end a nine-match goal drought.
The lead lasted just four minutes, though, as the unmarked Clark stooped low to head Westwood's free kick past Kasper Schmeichel for his first Villa goal since September 2012.
The hosts were dealt a blow before half-time when Westwood was carried off after a poorly timed challenge from Jamie Vardy - who received a yellow card.
Leicester also made a change at the break, with Ulloa coming off for David Nugent after failing to shake off an injury sustained in a strong challenge from Clark.
Villa created the better chances after the restart and Schmeichel did well to race off his line and force Benteke's shot to loop wide after the Belgium international held his run to latch onto Keiran Richardson's through-ball.
Nugent almost put Leicester ahead against the run of play in the 68th minute with a volley bound for the top-left corner of the net until Guzan did superbly to deny him with a fine save.
Villa deservedly moved ahead with just under 20 minutes remaining, though, when Benteke's excellent cross-field pass picked out Hutton's marauding run into the area, the right-back calmly slotting past Schmeichel at the near post.
Benteke was then twice denied by excellent point-blank stops from Schmeichel as Villa turned the screw before Leicester's task was made even more difficult when Konchesky saw red for a challenge on Hutton which resulted in the pair squaring up 11 minutes from time.
Hutton was cautioned for his reaction and Villa had to hold firm to withstand some late pressure, substitute Chris Wood coming closest with a stinging half-volley from the edge of the box that went wide as Nigel Pearson's side were beaten again.