The hosts came into the encounter off the back of two thumping wins which saw them score 10 goals, with the latter of those victories helping them reach the Copa del Rey final at the expense of their Clasico rivals Barcelona.
Both those games saw Karim Benzema bag a hat-trick, but their opener was charged by another member of the frontline.
Marco Asensio drove upfield and fed Vinicius Junior, whose cutback was played across the face of goal by Asensio, with the ball ultimately ricocheting into his own net off the unlucky Pau Torres.
Shortly after that setback for the visitors, Alex Baena scuffed an effort from the edge of the box into the grateful arms of Thibaut Courtois and the reigning champions quickly broke.
Benzema forced Pepe Reina into a smart save, before the former Liverpool goalkeeper prevented Rodrygo from dinking over him after Aurelien Tchouameni had regained possession and slipped in the 22-year-old.
However, the Yellow Submarine were offering a threat, especially in the form of livewires Chukwueze and Baena.
Sure enough, it was Chukwueze that equalised as Giovani Lo Celso played a slide-rule pass into the Nigeria international, who turned Nacho Fernandez inside out before firing home low to Courtois’ right.
Benzema’s miscued header from Asensio’s cross was the last action of a breathless first half, but Vinicius bailed out his teammate soon after the restart.
Dani Ceballos shook off the attentions of Juan Foyth and found the Brazilian, who received possession under pressure from Manu Trigueros and drifted into the area as Chukwueze and Aissa Mandi failed to provide any defensive protection, allowing their opponent to glide through and finish coolly.
Eventually though, Quique Setien’s men soon got the leveller that their first-half play merited.
Baena spread the play to Chukwueze and the winger jinked inside before delivering a cross that Jose Luis Morales swept home at the second time of asking, and although Chukwueze was initially ruled to have been offside, VAR overturned that decision.
Chukwueze was on a one-man mission to decide the outcome and produced the standout moment in the match, moving infield before brilliantly arrowing into the top corner from 25 yards, leaving a desperate Courtois unable to get a glove on it.
VAR would again came to the rescue of the 2021 Europa League winners in the closing stages when Mandi was eventually adjudged not to have handled in his own box, and despite ferocious home pressure, Setien’s side held out for a famous triumph that leaves Los Blancos’ slim chances of retaining their title in tatters.
Flashscore Man of the Match: Samuel Chukwueze (Villarreal)
