Villarreal topped Group F, securing their place in the last 16 in the process, after a five-goal thriller in France.
They took the lead after 36 minutes after Gerard Moreno scored from the penalty spot, but just sixty seconds later, the hosts equalised courtesy of Lorenz Assignon.
Ilias Akhomach made it 2-1 in the second half, but Ludovic Blas equalised against for Rennes. However, Dani Parejo won it late on for the Yellow Submarine, as the hosts had a 102nd minute goal ruled out by VAR.
Rennes XI: Mandanda, Matic, Bourigeaud, Terrier, Enzo Le Fée, Christopher Wooh, Bertuğ Yıldırım, Lorenz Assignon, Arthur Theate, Jeanuël Belocian, Mahamadou Nagida
Subs: Geoffrey Lembet, Gauthier Gallon, Santamaria, L.Blas, Gouiri, Warmed Omari, Muinga, Fabian Rieder, Adrien Truffert, Guéla Doué, Désiré Doué, Ibrahim Salah
Villarreal XI: Reina, Albiol, Capoue, Parejo, G. Moreno, Alexander Sørloth, Gabbia, Foyth, Álex Baena, Adrià Altimira, Ilias Akhomach
Subs: Femenia, Coquelin, Trigueros, Moreno, Morales, Ben Brereton Díaz, Jorge Cuenca, Iker Álvarez, Filip Jörgensen, Ramón Terrats
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