Two second-half goals Mohamed Salah and Trent Alexander-Arnold gave the Reds their first home win since December as Alexander-Arnold's late strike secured the win.
Ollie Watkins put Villa in front before Salah cancelled out his goal 10 minutes into the second half
Watkins struck on the brink of half-time after he outmuscled Ozan Kabak and saw his effort squirm into the far corner as Alisson failed to react.
The Video Assistant Referee will come under immense scrutiny once again after it ruled out Roberto Firmino's equaliser for an offside in the build-up.
As the lines were drawn many were in disbelief how it was offside.
Liverpool were level as Andy Robertson's strike was parried in the path of Salah who headed home.
With the game hanging on a knife-edge, the ever scrutinised Alexander-Arnold turned up when they needed him most.
The win sends Liverpool into the top four, for the time-being.
Liverpool dominate but VAR and Watkins take control
There was an early opening that was squandered by the Reds, Mohamed Salah pounced on Tyrone Mings' mistake but he failed to fire past the onrushing Emi Martinez.
Liverpool continued to push, after some nice interplay, Roberto Firmino found space on the edge of the box but flashed his effort wide.
Aston Villa fought back with attacks on their own, albeit few and far between but they had a glimmer on goal. Ezri Konsa found himself unmarked but his header easy for Alisson, a let-off for the hosts.
Similarly to the Arsenal game, seven days ago, Liverpool enjoying a lot of the chances but Salah and Jota both firing over and straight at Martinez.
Failing to make chances pay, Watkins created a yard of space and his effort squirmed beneath Alisson.
Once again VAR comes to haunt Liverpool. After some pinball in the box, the ball falls to Roberto Firmino who lofts over Martinez. However, they pull it back for a marginal offside.
5: Fierce effort from Salah but dealt with by Martinez.
Still some passages of play breaking down as a result of a poor pass.
Liverpool working the ball well and finding pockets of space.
Typical. Liverpool have the greater quantity of chances, Villa have a chance and take it.
Unlike Tuesday, they pressed well and forced Villa to relinquish possession cheaply.
Trent to the Rescue
Liverpool returned from the break and showed no signs of letting up despite VAR's error. 10 minutes after the restart, a well-worked move from the Reds saw Andy Robertson's effort parried but only as far as Salah who headed home.
The game was nearly tipped back in the Midlands-side favour as Trezeguet rattled the post with his effort from Watkins' cut-back.
With the match finely poised edging towards conclusion a moment of brilliance from Alexander-Arnold.
Thiago was first denied by a brilliant piece of goalkeeping from Martinez but it fell to the full-back who took it on his right-foot and fired into the far corner.
I said it on Tuesday, I'll say it again. Cometh the hour, cometh Mo Salah.
62: Close from Trezeguet, wow.
Very scrappy in parts, hard to get a foothold in the game after the equaliser.
LFC Transfer Room Verdict
Chances have to be taken, it's as simple as that. The first half was full of half-chances, whether it was down the throat of Martinez or too high.
Watkins goes down the other end and holds off Ozan Kabak before squeezing his effort beneath Alisson. Question marks have to be asked about the goalkeeping, maybe he was flat-footed or whatever who knows but a shot-stopper of his quality needs to keep it out which I'm sure he'll be beating himself up over.
Obviously, VAR will overshadow the result in what was, once again, another catastrophic mistake from Stockley Park. What a coincidence that it falls against Liverpool. How can you give it offside? I will never, ever know, fine margins which could affect a season. But, as previously mentioned, chances needed to be taken...
But it doesn't matter, what a goal Trent Alexander-Arnold. Slate him all you want, what finish.
Liverpool vs Aston Villa: Match Facts
Liverpool: Alisson; Alexander-Arnold, Phillips, Kabak, Robertson; Milner, Fabinho, Wijnaldum; Salah, Firmino, Jota.
Aston Villa: Martinez; Cash, Konsa, Mings, Targett; Douglas Luiz, Nakamba; Traore, McGinn, Trezeguet; Watkins
Goals: 55' Salah, 90+ Alexander-Arnold; 42' Watkins
Bookings: 65' Milner, 74' Robertson; 24' Konsa, 48' Luiz, 73' Targett, 85' Watkins
Subs: 70' Thiago (on for Wijnaldum), 75' Mane (on for Firmino), 89' Shaqiri (on for Kabak); 65' Barkley (on for Nakamba), 67' El-Ghazi (on for Traore), 82' Ramsey (on for Trezeguet).