Villa were two goals to the good at the break thanks to Benteke’s long-range effort and Andreas Weimann’s superb goal following more good work from Benteke.
Man of the match Benteke added a third soon after the restart before Liverpool grabbed a late consolation two minutes from time through captain Steven Gerrard.
Liverpool started off brightly, but for all their fine approach play they could not find a way past a stubborn Villa rearguard.
Villa stunned the home side when they broke the deadlock against the run of play on 29 minutes with a fine strike from Benteke.
There did not look much on when Benteke picked up a pass from Brett Holman 25 yards from goal, but the striker fired in a shot which clipped the inside of the right-hand post to beat Pepe Reina.
Four minutes later Villa were inches away from doubling their lead when Weimann capitalised on hesitant defending from the home side and chipped his effort over the stranded Reina only to see his effort land on top of the crossbar.
Liverpool continued to huff and puff as they tried to get back into the game, but it was Villa who doubled their advantage five minutes before the break with a superb goal from Weimann.
Weimann played a ball into Benteke inside the box and the striker brilliantly backheeled the ball back into the path of his strike partner who drilled his shot under Reina to send the visiting fans into raptures.
After a bright start to the second half from the home side, with Daniel Agger having a penalty claim waved away and Luis Suarez and Stewart Downing both seeing efforts saved by Brad Guzan, Villa put the game beyond Liverpool on 51 minutes with a third goal as Benteke netted his second of the contest.
Joe Cole was robbed of the ball inside his own half and Benteke burst past the two weak challenges from Martin Skrtel and Joe Allen before finishing from inside the box high into the net past Reina.
Liverpool pushed forward in a bid to get back into the game and they had two further shouts for a penalty for handball waved away by the officials.
The home side grabbed a consolation two minutes from time as Gerrard diverted Glen Johnson’s shot into the net past Guzan, but it was too little too late for Liverpool as Villa eased to all three points.