A Chris Brunt stunner and a Fabian Delph own goal inside the first nine minutes got the Baggies off to a flyer at Villa Park but the hosts replied quickly through Andreas Weimann, Leandro Bacuna and Delph.
Youssouf Mulumbu made it 3-3 at half-time but Benteke secured only Villa’s third Barclays Premier League home win of the season from the spot after the striker himself was fouled.
The result left new West Brom manager Pepe Mel still waiting for his first victory in the job.
The performance of his side’s defence might also have raised concerns for a side that has now won just once in 13 league games.
In possession, they did arguably have the better of the game in the second half but they could not add to their first-half tally.
ASTON VILLA: Guzan, Lowton (Holt 65), Vlaar, Clark, Bertrand, Bacuna, El Ahmadi (Sylla 77), Westwood, Delph, Weimann (Baker 80), Benteke.
WEST BROM: Foster, Reid (Berahino 76), Lugano, Olsson, Ridgewell, Morrison, Yacob, Mulumbu, Brunt, Anichebe (Vydra 80), Anelka (Amalfitano 26).
Referee: Mark Clattenburg.