Unai Emery sprung a slight surprise by fielding a full-strength side just five days before the UEL showdown with Freiburg, but the gamble almost paid dividends straight away, when Ollie Watkins linked up with Morgan Rogers and flashed a shot at Giorgi Mamardashvili, who saved well.
The striker was in again minutes later, but he slipped and landed awkwardly, with Villa Park holding its collective breath until he gingerly returned to his feet.
There was another nervous moment for the home crowd when Liverpool had the ball in the back of the net, with Cody Gakpo following up after Emiliano Martínez could only parry Ryan Gravenberch’s effort, but the offside flag went up at once.
The visitors grew into the ascendency as the half wore on, but it was Villa that broke the deadlock just before the break with a well-worked short corner.
As has been the case so often before tonight, the Reds found themselves caught cold by a set piece routine, leaving Rogers with time to curl the ball artfully into the corner.
But for all their nervousness at the back, Liverpool showed their own ability from the dead ball, and restored parity early in the second half, after Virgil van Dijk got on the end of a wicked Dominik Szoboszlai delivery.
Rio Ngumoha then almost completed a rapid-fire turnaround, but his curling effort struck the post, and Gakpo could not convert the rebound despite the flag staying down this time This proved costly in no time at all, when a Szoboszlai slip allowed Rogers to release Watkins, who finished smartly to make it 2-1.
Soon after, Mamardashvili called into action to deny Watkins a second, and Emiliano Buendía then came agonizingly close from the edge of the box, whipping his effort onto the underside of the crossbar.
But it seemed to be a matter of time – and so it proved, with Watkins becoming the grateful recipient of a tap-in after two more saves from the Liverpool stopper. However, that was not the end of the scoring, with John McGinn supplying the icing on the cake by curling a stunner into the top corner, before Van Dijk provided the most low-key of consolation goals in stoppage time.
Liverpool will still secure a scarcely-merited UCL spot if Man City beat Bournemouth on Tuesday, and at worst will have the chance to earn it by beating Brentford on the final day of the season.
Meanwhile, having beaten the Reds for just the second time in 17 meetings, Aston Villa can now turn their full focus to Istanbul, and ending a 30-year trophy drought, alongside claiming their first major continental honours this century.
Flashscore Man of the Match: Ollie Watkins (Aston Villa)
