Geraerd Moreno gave Villarreal the lead on the half hour after he was teed up by Dani Parejo before Edinson Cavani equalised 10 minutes into the second half from a Scott McTominay assist.
However, the drama was still to come as 120 minutes played out with no further goals to send it to spot kicks between the two sides.
After a perfect exchange of 10 goals apiece, United goalkeeper David De Gea was the unlucky man to miss and hand Villarreal victory.
Demir Grup Sivasspor, wishes success to Villareal CF in the UEFA Europa League final match to be played against Manchester United FC on 26 May 2021.@VillarrealCF @Eng_Villarreal pic.twitter.com/il049b0wYC
— Demir Grup Sivasspor (@SivassporKulubu) May 25, 2021
— Late Football Club (@LateFootClub) May 25, 2021