Marcos Llorente scored twice in extra-time to knock Liverpool out of the Champions League and see Atletico Madrid progress into the quarter-finals after a 3-2 win on aggregate.
Llorente equalised after Roberto Firmino gave the Reds the lead of the tie in the 94th minute and scored again just before the break of extra-time.
Alvaro Morata scored on the counter-attack in the 120th minute for the visitors and put the game beyond any doubt whatsoever.
Georginio Wijnaldum gave Liverpool the lead on the night with a first-half header and levelled the tie after a 1-0 Atletico win in Madrid.
Jordan Henderson returned to the Liverpool side after the captain limped off injured in the first-leg three weeks ago in Madrid.
Record-signing Joao Felix was back in the Atleti side after making his return from injury, and started alongside former Chelsea striker Diego Costa.
Costa was involved just 10 seconds in when he was played through by Felix but the striker’s shot went wide of Adrian’s goal.
The Reds then went close when Trent Alexander-Arnold found Wijnaldum’s head but his effort was too close to Jan Oblak on five minutes.
The hosts had a couple of half-chances with Mohamed Salah and Jordan Henderson both striking their efforts off target.
It was Atleti who had the next opportunity when Felipe met a Koke corner but the defender’s near-post header went just wide.
One of Liverpool’s best chances of the first-half fell to Sadio Mane, who was laid off by Salah, but the forward’s shot was straight at Oblak.
Another great chance for the Reds was just moments after when Alexander-Arnold’s dangerous cross was parried away brilliantly by Oblak.
On 43 minutes, Liverpool finally had their breakthrough, when Wijnaldum headed in an Alex Oxlade-Chamberlain cross.
Salah had a great chance for the hosts once the second-half restarted but hit it straight at Oblak’s gloves from a tight angle.
Roberto Firmino had a glorious chance for Liverpool at the far-post following an Alexander-Arnold delivery but Oblak again was equal to it.
Andy Robertson hit the crossbar after a Salah shot fell on the Scotland captain’s head and cannoned back out.
Robertson had another chance as Oblak stopped an Alexander-Arnold shot and the ball fell back to the left-back but Kieran Trippier blocked his shot.
Mane had a chance with just five minutes of normal time remaining when his acrobatic effort went marginally over the crossbar after a Wijnaldum header found the Senegalese winger.
Salah then went close after an excellent solo run found him just inside the box but his left-footed strike went over the bar.
The game was level on 90 minutes, meaning there would be another 30 minutes of extra-time at Anfield.
Oblak was called into action early in extra-time when Wijnaldum’s powerful low shot was well saved by the Atletico goalkeeper.
Firmino put the Reds in the lead of the tie for the first time after hitting the post with a header and fortunately it fell back to the Brazil striker who put it in the empty net.
However, moments later a mistake from Adrian saw Llorente side-foot home from long-range to put Atletico in the driving seat.
Llorente then scored a similar goal after a counter-attack from the visitors and put the game beyond the Reds.
Morata went down the other end when all the Liverpool players were up pitch and hit it low and firm past Adrian to win the game on the night for Atletico.
Atletico executed their extra-time plan to perfection and will be in the hat for the quarter-final draw with last season’s champions knocked out of the competition.