Amir Rrahmani scored in the 8th minute, then Georges Mikautadze (23rd) and Santiago Mouriño (26th) turned the game around before Tani Oluwaseyi added a third goal in the 86th minute.
Napoli lost their second consecutive league-phase game, leaving them on zero points after two matches in the Champions League.
The win gives Villarreal its first three points of the 2026-27 Champions League and its first European victory since the March 2024 Europa League match.
Massimiliano Allegri said his side conceded too many chances and goals, and called for more defensive sacrifice without the ball.
Amir Rrahmani put Napoli ahead in the 8th minute, finishing from close range after a corner routine that Luiz Júnior had partly stopped. Napoli controlled the opening stages, and Rasmus Hojlund hit the crossbar with a header in the 22nd minute. The match then turned quickly. A weak pass back by Matteo Politano was intercepted by Georges Mikautadze, who slotted the ball into an empty net in the 23rd minute. Two minutes later, a gap opened on the Napoli left after a mix-up between Giovanni Di Lorenzo and Benoit Badiashile, and Santiago Mouriño struck from distance to make it 2-1 in the 26th minute. Villarreal led at the interval.
After the break Villarreal kept pressing, and Napoli's attacks lacked punch. Allegri sent on David Neres, Noa Lang and Leonardo Spinazzola around the hour mark, but the Villarreal side kept the ball away from the Napoli penalty area. Hojlund got in behind the defence and tried a right-foot shot from a wide position in the 36th minute, which the goalkeeper stopped. Tani Oluwaseyi made it 3-1 in the 86th minute, finishing after a pass from Ayoze Pérez. Napoli's second straight defeat in the competition ended with that score.
Massimiliano Allegri spoke to Sky Sport microphones after the game. He said he had asked Kevin De Bruyne to move into the middle of the attack, because of his quality, but that the message had not got through. Allegri pointed to the defending as the problem.
“You cannot concede a goal as if it were nothing.”
He went on to criticise the way his side had defended, and said the team needed more sacrifice when it did not have the ball.
“It now seems to have become a disgrace to know how to defend, but if you concede shot after shot, you run a risk.”
Napoli remain on zero points in the league phase after two games. Villarreal collected its first three points of the season in the competition and its first European win since the Europa League match in March 2024. Napoli will next host Bodo/Glimt at the Maradona stadium on Tuesday, 20 October.
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Amir Rrahmani gave Napoli the lead in the 8th minute, but Villarreal turned the match around with two goals in three minutes and Tani Oluwaseyi sealed the win in the 86th minute at La Cerámica.
AI text based on reports by ANSA.it, Adnkronos, Il Messaggero and other publishers. Changed .