Villarreal qualified for the knockout stages after beating Tottenham Hotspur 2-0 at Stevenage to end their Group F campaign with a perfect record.
Christian Cedres Artiles curled in the 31st-minute opener, before Roger Riera scored from close range in stoppage time at the end of the first half.
Spurs goalkeeper Alfie Whiteman saved well from Dario Poveda and Franco Acosta to prevent the Spanish side adding a third.
In second-half stoppage time, Acosta and Spurs duo Keanan Bennetts and Simon Moreno were sent off after an altercation.
Villarreal are six points clear at the top of Group F after three wins out of three. Spurs are second, with three points from two matches, and a win over Benfica in their final match will secure qualification.
See: Spurs report
Next fixture
Spurs: 18 Nov v Chelsea (H) PL2
