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The Reds went into the semi-final second leg with a two-goal advantage following last week's win at Anfield.
But their lead quickly evaporated after Villarreal scored two first half goals thanks to Boulaye Dia and Francis Coquelin.
Dia opened the scoring in just the third minute, with Coquelin netting just before half time.
However, Jurgen Klopp's men delivered a much better performance after the break - with Liverpool scoring three second half goals.
Fabinho made it 2-1 on the night after firing a low strike through the legs of Geronimo Rulli.
Luis Diaz, who lit up the second half following his introduction into the game, headed home to make it 2-2.
Sadio Mane completed the comeback, rounding the on-rushing keeper to slot into an empty net to make it 3-2 (5-2 on aggregate).
Mane passes the ball into an empty net after rounding Gerónimo Rulli! ⚽️— Football on BT Sport (@btsportfootball) May 3, 2022
Liverpool have turned this around with such ease in the second half!
Three goals in the space of 12 minutes 🌪#UCL pic.twitter.com/XsohPejL2j
Klopp's side will face either Manchester City or Real Madrid in the Champions League final on May 28.
It will be Liverpool's third Champions League final appearance in five years, having lost to Real Madrid in 2018 and beaten Tottenham in 2019.
Featured Image Credit: BT Sport/Champions League
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