The visitors opened the scoring inside 10 minutes as Gabriel Agbonlahor pounced on a loose ball inside the area to poke home what proved to be the winner.
Liverpool dominated possession but could not find a breakthrough, with Philippe Coutinho going closest when his effort came back off the post.
Here, Sports Mole takes an in-depth look at whether Villa deserved a victory which keeps them unbeaten in the league this season.
On target: 1
On target: 1
Was the result fair?
The stats suggest that this was something of a smash and grab job from Villa, but that wasn't really the case. They started the match very brightly and deserved their early lead when Agbonlahor poked them ahead. Indeed, it could have been more had Philippe Senderos converted when left unmarked from a free kick in the 13th minute.
After such a positive start, though, the visitors retreated into their shells and allowed Liverpool to control possession and dictate the tempo of the match. Villa were more than happy for that to happen as they got bodies behind the ball, frustrating the hosts, who could not find a way through.
The Reds were dominant, though, and hit the post late on through Coutinho's curling effort. They created nowhere near as much as they should have done considering how much of the ball they saw, but they certainly deserved a point from this game. A draw would have been the fairest result, but Liverpool were made to pay for their slow start.
For a team that scored 101 goals last season, it is hard to fathom how they had 75% possession and 18 shots yet tested Brad Guzan just once. Of course, Luis Suarez is now long gone, while neither Daniel Sturridge or Raheem Sterling were fit enough for the starting lineup, but even so Liverpool should have had enough quality in their ranks to create more than that.
They were overrun in the opening 20 minutes or so, with Villa breaking forward freely and winning corner after corner. It was set pieces that really troubled the hosts as they simply couldn't deal with Senderos and company. They soon grew into the game and took complete control, but their attacks were slow and methodical as opposed to the quick breaks were are used to seeing from Brendan Rodgers's side.
There was a lack of creativity in the final third as Villa packed out the middle of the park. There is no doubt that the visitors used spoiling tactics for more than an hour this evening, but as title contenders Liverpool need to be able to overcome that. They couldn't do that today, and that is something that Rodgers will need to address. This was a hugely disappointing result and performance from his side.
Aston Villa's performance
Paul Lambert will be absolutely delighted with his side tonight. Not only did they pick up an unexpected three points, but the performance was sensational from the visitors. They began the match really well and should have been 2-0 ahead inside 15 minutes as they continued to cause the Liverpool defence problems from set pieces.
From a neutral point of view, it was disappointing to see Villa step off the front foot and not push for a second. Instead, with around 20 minutes on the clock, they parked the bus and began time wasting, despite there being so long to play. It was a questionable decision, but it turned out to be a good one as Villa defended valiantly to keep hold of their lead.
It was not pretty nor entertaining for fans of pure football, but it was effective from the visitors. They worked incredibly hard off the ball, and every single player was fully committed to the cause. From Agbonlahor up front to Nathan Baker and Senderos at the back, they never afforded Liverpool's dangermen the time that they needed, and in the end it was a textbook rearguard action.
Sports Mole's man of the match
Philippe Senderos: Lambert got some stick for bringing Senderos to the club this summer, but he has started his Aston Villa career very well. In the absence of the injured Ron Vlaar, Senderos and Baker stepped up to the plate with titanic defensive performances, clearing everything that came their way.
Senderos was also an attacking threat as Liverpool struggled to deal with him from set pieces, and it was his strength that led to the winning goal. He should have scored himself soon after, but he more than made up for that miss at the other end. Agbonlahor and Baker could have also won this award, but Senderos's impact at both ends of the field sees him nick it.
This one goes to Dejan Lovren for his marking in the build-up to the only goal of the game. The defender was too tight to Senderos, who simply overpowered him to win the first ball. There was a little luck involved as the ball fell to Agbonlahor, who poked it home, but it was poor defending from the summer recruit. Senderos also deserves a mention here for his miss, but that didn't prove to be as decisive as Lovren's marking.
Lee Mason had a fairly straightforward evening today, dishing out just three yellow cards and not having a really big decision to make. He did miss a trip by Senderos on Mario Balotelli off the ball, but that was just about the only blotch on his record today.
Liverpool: Champions League football returns to Anfield on Tuesday as Liverpool host Ludogorets Razgrad in their first match in the competition for five years.
Aston Villa: Villa, meanwhile, will be looking to build on this victory when they host Arsenal on Saturday.