Villarreal secured their first Champions League win in eight matches after coming from behind to beat Napoli at the Estadio de la Ceramica.
The La Liga side had suffered seven consecutive defeats in the competition since drawing 2-2 with Juventus in October 2025.
After a narrow 3-2 defeat by Borussia Dortmund on the opening matchday, Villarreal looked set to become the first Spanish side to lose eight consecutive European matches when defender Amir Rrahmani found space at the back post to put Napoli ahead in the eighth minute.
The visitors almost doubled their lead in the 22nd minute, but Rasmus Hojlund’s header struck the crossbar.
Less than 60 seconds later, Villarreal drew level through Georges Mikautadze, who scored his first Champions League goal of the season after pouncing on an underhit backpass from Matteo Politano.
Villarreal took the lead in the 25th minute when Uruguay midfielder Santiago Mourino arrowed a strike from distance past Vanja Milinkovic-Savic.
Substitute Tani Oluwaseyi then ensured Villarreal ended their run of seven consecutive defeats with a composed finish from inside the area four minutes from time.
Villarreal travel to Liverpool on 20 October (20:00 BST), while Napoli host Bodo/Glimt at the same time.