A feverish contest brimming with end-to-end action was initially going the visitors' way, as Emiliano Martinez's horrific own goal, Cody Gakpo's strike and a Jarell Quansah header would seemingly render a Youri Tielemans strike inconsequential.
However, just as it appeared that Jurgen Klopp's last away game in charge of the Reds would end in success, Duran had the last two laughs with an unbelievable double in the final five minutes, leaving Unai Emery's men on the cusp of Champions League qualification.
Five points clear of Tottenham Hotspur in fourth place, the Lions will dine at Europe's top table next year if Spurs fail to win both of their last two matches, starting with Tuesday's blockbuster battle with Manchester City.
Meanwhile, Liverpool have already been assured of their third-placed ranking in the table and ought not to reflect on their late capitulation too much, as all eyes are now on Klopp's Anfield farewell against Wolverhampton Wanderers this weekend.
After his standout performance against Tottenham Hotspur last weekend, Harvey Elliott was unsurprisingly trusted from the off once more by Jurgen Klopp, who did see reasons to bring Joe Gomez in at left-back.
Ten of Villa's starters from their Europa Conference League heartbreak against Olympiacos held their places - the only alteration was Matty Cash out for the fit-again Tielemans - but it was one of the hosts' normally reliable stalwarts who produced a horrible howler just two minutes in.
A slick link-up between Elliott and Mohamed Salah down the right ended with the former delivering a cross, which took a slight nick off of Pau Torres but would seemingly fall into Martinez's grateful grasp.
Villa rue individual blunders in chaotic first half
However, the Argentine inexplicably let the ball slip from his gloves, and in his desperate attempts to claw the ball away from the goal-line, he inadvertently punched it over the line for a farcical own goal.
The Reds rash was all over a beleaguered Villa in the opening minutes, but as the visitors failed to make their early dominance count for a second goal, the Lions put the frenetic game back to square one in the 11th minute.
Prolific finisher and provider Ollie Watkins was the instigator, racing away from Quansah on the left towards the byline and playing a smart ball into space, which Youri Tielemans arrived unmarked to meet before firing in a crisp low strike.
The hosts' hard-earned reprieve would not last for long, though, as in the 23rd minute, Gomez and Gakpo just about kept themselves onside - confirmed by a lengthy VAR review - as the Dutchman converted the defender's low cross at the back post.
With Gareth Southgate and lifelong Lion Tom Hanks watching on, Villa were still making inroads and should have pegged the Reds back again in the 36th minute, but Diego Carlos inexplicably missed an open goal from one yard out.
Leon Bailey's ball across the six-yard box was on the money for both Carlos and Watkins - who were jostling for position inside the six-yard box - but the former embarrassingly scuffed his shot in what will go down as one of the worst misses in the history of the Premier League.
It was just the 0.99 Expected Goals (xG) for that chance by Carlos, justifying Dorival Junior's decision not to call him up to the Brazil squad for the 2024 Copa America, as Liverpool edged a frenzied opening 45.
The first half was a sign of things to come in the second, as the visitors established a two-goal advantage just three minutes after the restart through Quansah, who produced a magnificent leap to meet Elliott's free kick and directed a soaring header past a stranded Martinez.
Duran Duran and Liverpool come undone
However, Emery's men thought that they had cut the deficit down to one in the 52nd minute, when Bailey raced beyond the Reds backline and squared for Watkins to finish, but the Jamaican winger had just gone slightly too early and - for whatever reason - took his frustrations out on Watkins.
Douglas Luiz was the next to have a pop at the Englishman in the 54th minute, where Alisson Becker's horrendous pass fell to Moussa Diaby; the Frenchman managed to poke the ball into the centre where Luiz was waiting for the finish, but Watkins instead attempted an audacious backheel, which did not come off.
There was barely a moment for either set of defenders to catch their breath - a combination of Salah and Elliott then bundled the ball over the line in the 59th minute, but Luis Diaz was just caught offside as he sped through before providing the cross.
As the second half progressed, however, Villa's forays forward were becoming few and far between, with Liverpool firmly in control of the result without threatening a fourth too much, and the Lions' cause was not helped by an injury to Nicolo Zaniolo just 12 minutes after coming on.
However, in the 85th minute, it was Alexis Mac Allister's turn to make a fatal error, as the Argentine cheaply lost possession to Calum Chambers in a dangerous area and was powerless to prevent Duran from emphatically finding the bottom corner from inside the D.
Duran's strike sparked a nerve-jangling finale, in which Darwin Nunez put the ball in the back of the net in the 87th minute but was also caught out by Villa's high line, but the next goal - incredibly struck just two minutes later - would count.
Still full of energy and vigour, Diaby surged forward towards the Liverpool box and successfully picked out the run of Duran, who saw the Frenchman's pass ricochet off his thigh and loop into Alisson's goal to complete an astounding turnaround.
The roaring Lions were gifted nine minutes to try to find a Champions League-clinching winner, the third of which saw Alisson make a fantastic one-on-one save from Diaby, and late Lions penalty appeals for a Virgil van Dijk handball were waved away before the curtain closed on a captivating contest.