Samuel Chukwueze was on target for as he scored the only goal for Villarreal to send off Sivasspor in Group I on Thursday.
Chukwueze scored 15 minutes before the end of the game and was replaced a minute later.
Villarreal win at Sivasspor guarantees the La Liga side a place in the round of 32 with just one game left to play.
In Group G, Wilfred Ndidi returned to Leicester City action after a long injury absence.
The Premier League side lost 1-0 to Zorya in Ukraine.
Ndidi has been out since September, was replaced in the 56th minute while Kelechi Iheanacho all of the 90 minutes.
Meanwhile, Leicester remain top of the group despite losing to Zorya.
In Group K, Chidera Ejuke featured for CSKA who lost 1-0 at home to Wolfsberger.
Ejuke came off the bench in the 46th minute of the game but couldn’t help his side which remain bottom of the group with three points.
In other fixtures, LASK held Tottenham Hotspur to a 3-3 draw, AC Milan beat Celtic 4-2 and Lille edged Sparta Prague 2-1.