Cristiano Ronaldo
It was a repetition of last season's Europa League final and the Yellow submarine edged past Manchester United on penalties but Ronaldo proved the difference in the two squads.
Paco Alcacer gave Villarreal the lead shortly after halftime and the game was heading to a loss for Ole Gunnar Solskjaer's men.
Alex Telles, who is playing for injured Luke Shaw, volleyed in a brilliant equaliser on the hour.
It seemed all over at both teams sharing the spoils until Ronaldo struck right at the death as United bounced back from an opening group stage defeat by Young Boys.
Manchester United now turn attention to the Premier League as they welcome Everton to Old Trafford.
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