With the tie level at the end of the 90 minutes thanks to Georginio Wijnaldum’s header, Roberto Firmino looked to have scored the tie-winning goal just four minutes into extra time.
But two goals from substitute Marcos Llorente in the space of eight minutes, the first courtesy of a howler from stand-in keeper Adrian, drew the sides level on the night and gave Atletico the lead on aggregate.
Anfield was stunned into total silence as coach Jurgen Klopp looked bemused on the touchline, arms held out disbelievingly.
Alvaro Morata scored the third in the final few seconds to secure a memorable 4-2 aggregate win for Atletico.
This stadium had been the site of one of the greatest ever Champions League comebacks last season, as Liverpool overturned a 3-0 first-leg deficit against Barcelona to reach the final.
Tonight, it’s the site of one of Liverpool’s most painful European defeats.
Pantomime villain
There would have been more than a few hearts in mouths inside the opening 20 seconds at Anfield, as Joao Felix’s slick turn and pass set Diego Costa through on goal.
The Spanish striker, a familiar foe for Liverpool from his time at Chelsea, could only skew his shot into the side netting but it was an early reminder for Liverpool of the quality that Atletico Madrid possesses going forward.
Costa was soon slipping into his preferred role of pantomime villain, petulantly throwing the ball away as Liverpool goalkeeper Adrian attempted to take a quick free-kick.
It was a tactic Atletico had been expected to employ in an attempt to frustrate both the Liverpool fans and players into submission and reduce the game to a scrappy affair.
They succeeded in doing exactly that but Liverpool was giving as good as it was getting, ferociously snapping into tackles with
From the outset, Anfield wasn’t quite at its famous levels of noise — perhaps the torrential rain had dampened the atmosphere somewhat — but Wijnaldum’s stinging strike, palmed away brilliantly by Jan Oblak, was enough to spark the crowd into life.
As had been expected, Liverpool dominated possession inside the opening 30 minutes but, Wijnaldum’s effort aside, hadn’t troubled Atletico’s back line.
Diego Simeone’s side is widely considered the best defensive unit in European football and as Liverpool’s attacks were repelled again and again, it sometimes felt as though it was crossing balls into a brick wall.
But Liverpool’s pressure eventually started to tell and a few of those bricks started coming loose; Wijnaldum once again tested Oblak before he eventually found a way through.
Alex Oxlade-Chamberlain’s cross found the Dutchman totally unmarked in the middle of the penalty area and he directed his header down into the wet turf and into the top corner.
Wijnaldum is making a habit of scoring big goals for Liverpool in the Champions League; last season, he scored a brace to haul Liverpool level in that famous semifinal comeback win against Barcelona.
Anfield roared into life and Atletico’s players spent the remaining two minutes of the first half desperately waiting for the half-time whistle to blow.
Backs to the wall
Those 15 minutes respite changed very little and Atleti’s players were back out in the second half and immediately had their backs to the wall.
Again they had Oblak to thank for keeping them level in the tie, as the Slovenian stopper did brilliantly to save efforts from Oxlande-Chamberlain and Roberto Firmino.
But midway through the second half, Liverpool was given a sharp warning of how quickly this tie could change.
Felix, Atletico’s $142 million star signing, managed to wriggle free on the edge of the area and his deflected effort brought an awkward save out of Adrian.
Liverpool’s stand-in keeper should have dealt with the effort comfortably but presented Angel Correa with an opportunity from his weak parry, though he did eventually manage to smother the ball.
With little more than 20 minutes remaining, the whole of Anfield thought Liverpool had found the tie-winning goal.
After ricocheting around in the box, the ball found its way to Andy Robertson at the far post but Kieran Trippier did brilliantly to get a slight touch on the header and deflect it onto the crossbar.
In the dying seconds, totally against the run of play, Atleti thought it had found the winner.
Renan Lodi’s free-kick into the box was met by Saul Niguez’s thumping header into the top corner. The 3,000 Atletico fans behind that goal went wild, as did the entire Atleti bench, but their celebrations were cut short by the linesman’s flag for an obvious offside.
30 minutes of madness
Extra time started at a blistering pace and Firmino, with his first Anfield goal all season, looked to have secured passage through to the quarterfinals, reacting fastest after his header had hit the post to stab the rebound home.
But then it was the turn of Adrian to take center stage, the player called upon the least throughout the 90 minutes and as much of a spectator as the 60,000 fans inside Anfield.
The Spaniard’s scuffed clearance gifted the ball to substitute Llorente, who did brilliantly to bend the ball into the vacant far corner of the goal.
Then, just like that, it was two.
Some lazy defending from both Joe Gomez and Virgil van Dijk gifted Llorente with space on the edge of the area and he curled another unerring strike into the bottom corner.
Anfield was silent, save for the small pocket of delirious Atletico fans at the opposite end of the stadium.
With seconds remaining, Alvaro Morata popped up to score Atelti’s third and emphatically seal passage through to the quarterfinals.
There were tears from both sets of fans at full-time, only they were very different types of tears.