The Belgium striker was in inspired form, scoring two goals and setting up another as the visitors continued their good run and sealed a shock result against the profligate Reds
After the home side had wasted a series of goalscoring opportunities, Benteke found the bottom corner from outside the box to hand Paul Lambert's side the lead.
A wonderful piece of skill from the front man then allowed Andreas Weimann to sweep home from 10 yards, before Benteke parted the Liverpool defence to add a third shortly after half-time.
Steven Gerrard got a touch to Glen Johnson's low shot to finally break Villa's resistance in the final minutes, but it was too little, too late for the profligate Reds.
Benteke lead the line for a youthful Villa team that lined up in a 5-3-2 formation. Only three players in the starting line-up were above the age of 23 in the absence of the likes of Darren Bent, Ron Vlaar and Gabriel Agbonlahor.
Brendan Rodgers, meanwhile, recalled Luis Suarez to the Liverpool team following his one-match suspension. Jonjo Shelvey consequently switched to the left flank, with Jose Enrique sidelined by a hamstring injury.
At first, the trip to Anfield looked as if it might be too much for the young Villans. Their back five sat deep in their own half and invited pressure which Liverpool should have turned into a lead.
Suarez, as is usually the case, was at the centre of the best and worst of the Reds' attacking play. The Uruguayan failed to pick out either Gerrard or Raheem Sterling at the end of a three-on-one break but then nearly made amends by robbing the ball off Chris Herd. Shelvey was set to pull the trigger when Nathan Baker arrived with a brilliant sliding tackle.
Villa, though, now have a match-winning striker of their own. Their offensive threat had been minimal before Benteke nonchalantly pushed the ball out of his feet before rifling a low shot inside Pepe Reina's right-hand post from 25 yards.
The Belgian then turned provider to double the lead and leave the Liverpool supporters in a half-time state of shock. Racing on to a pass from Weimann, Benteke returned the ball to the centre of the box with a sublime back-heel to allow the Austrian to stroke home.
Benteke's rampage was only stalled by the interval. Minutes after the break, after substitute Joe Cole had been dispossessed in midfield, the 22-year-old simply marched past Martin Skrtel and into the Liverpool box before slotting past a helpless Reina.
Villa's defending was last-ditch throughout, but it was effective. Liverpool found the penalty area crowded with yellow shirts every time they entered it and Brad Guzan continued to vindicate Lambert's decision to leave Shay Given on the bench.
Eventually, the Villa wall was breached. Johnson cut in from right-back and swatted a left-footed shot across goal which Gerrard deflected past Guzan. The goal did little to improve the mood at Anfield, though, as Liverpool's unbeaten run was brought to an end.