Dani Parejo tucked away the rebound from his own saved penalty in second-half stoppage time to earn Villarreal a stunning 4-3 victory over Celta Vigo.
The result concluded an exhilarating evening at El Madrigal, which got started when Borja Iglesias opened the scoring for the visitors in the 12th minute.
Sergi Cardona equalised from a corner in the 26th minute, but the hosts restored their lead five minutes later when Oscar Mingueza scored directly from a free-kick.
Cardona turned provider after the break to set up substitute Thierno Barry, who drew the sides level one minute after his 59th-minute introduction.
A Jailson own goal sent Villarreal in front for the first time in the contest before Carl Starfelt nodded home Mingueza’s delivery in the 80th minute.
Just as it seemed the sides were set to share the spoils, Hugo Alvarez was caught dragging down Barry by his shorts and the hosts were awarded a spot-kick after a VAR check.
Ivan Villar denied Parejo’s initial effort but could not act quickly enough to stop the follow-up in the 10th minute of time added on.
The result sees the victors climb to the top of the LaLiga table with seven points from their first three league games, while Monday night’s losers sit second with six.
A brace from Dusan Vlahovic inspired Juventus to a 3-0 Serie A victory at Verona.
Nicolo Savona also scored on his first start for the visitors, while ex-Aston Villa man Douglas Luiz was once again named amongst Thiago Motta’s substitutes.
Juventus are now the only side to have secured victories in both of their opening two Italian top-flight encounters.
Some believed the contest would see a first start for Luiz after he was named as a substitute in Juventus’ season-opening win over Napoli.
He began his evening on the bench, and was introduced as a substitute in the 69th minute.
Vlahovic’s first came after some sloppy defending, the ball eventually making its way to Kenan Yildiz, who slipped a pass to the Serbian for a low 28th-minute finish from 12 yards.
Savona then opened his own account with a looping header from Samuel Mbangula’s cross in the 39th minute.
Seven minutes after the break, Jackson Tchatchoua was punished for his challenge on Mbangula and the referee pointed to the penalty spot.
Vlahovic made no mistake, sending Lorenzo Montipo the wrong way to make it three.
Patrick Cutrone netted How’s first Serie A goal in 21 years as they split the points in a 1-1 draw at Cagliari.
Atalanta loanee Roberto Piccoli headed home from close range in the 44th minute to open his account at Sardegna Arena.
Como-born Cutrone levelled in the 53rd minute when he tucked home Alberto Dossena’s nodded delivery to ensure last season’s Serie B runners-up picked up their first point of the campaign.
