Forced into a couple of smart stops by Messi, he was beaten all ends up by the Argentine's free kick but had the woodwork come to his rescue. Was turned inside out as Messi set up the winner.
Part of a defense that was strong throughout a tough opening 45 minutes. Looked ragged as Barcelona changed through the gears in the second period.
Wanted by Premier League clubs, it was easy to see why as he kept the one of the world's top players relatively quiet in the first half. Continued to thwart Barca until the final 10 minutes.
The pick of the home side's defenders at El Madrigal. He threw his body on the line to preserve parity in the opening stages and came close at the other end to giving his side the lead.
Turned in a commendable display with some important interceptions. His last-ditched defending almost got Villarreal off the hook but could do nothing to prevent the goal.
Strong running down the left flank caused some panic in the Barcelona defense. Miscued though when he found himself well placed to genuinely threaten.
Never wasteful when possession did eventually come his side's way. Extremely unlucky not to give his side the lead as his drilled effort came back off the post in the second half.
Tucked in to try and keep Barcelona's space on the right at a premium but that never helped defensively. Looked better going forward and was involved in Villarreal's best move at the end of the game.
Didn't provide the link-up play expected with the front pairing of Dos Santos and Cheryshev. Struggled to get into a scrappy first half and subbed off in the second.
Excelled in his role in the middle of the park, sitting deep and frustrating Messi for large parts of the game, forcing the Argentine into a wide position to find space.
G. dos Santos
Posed a genuine threat to his former club with his positioning and runs in behind. Sparkled late on as he struck the post and almost set up Vietto for a late goal.
Given little to do but often found himself beaten all ends up when the ball did come towards his goal. His woodwork was rattled three times but somehow his clean sheet was preserved.
Showed neat footwork when he was able to get forward down the left. Defensively, not asked much of down the flank but perhaps didn't exploit the space afforded to him as his side focused attacks down the opposite wing.
Strong at the back, had to keep an eye on Dos Santos on the occasions where Mathieu struggled. Made some important tackles in his own area to quell Villarreal attacks.
A genuine threat going forward down the right. Picked up a booking for protests following a heavy challenge. Delivered a number of crosses that asked questions of the Villarreal defense, but most were answered.
An eventful game for the center back that on another day could have ended in disaster. Hit his own post with a tackle and gave the ball away to Vietto inside his own box, but ultimately made his presence felt as they kept a clean sheet.
Positioned to win the ball in front of the back four, the midfielder found himself much higher up the pitch in the first half as Barcelona pressed. Still fulfilled his duty well and mopped up loose balls.
An uneventful display for the Brazilian as he failed to aid the visitors in their search for a break in the deadlock. Showed composure on occasions outside of the final third.
Another strong performance from the former Sevilla man. Delivered a number of teasing crosses and tested the fingertips of Asenjo more than once.
The key to everything good about this Barcelona display. There weren't many chances but those that came about were largely down to the Argentine's industry.
Didn't get the chance to add to his opening day goal. Found the ball at his feet in the area on all-too rare an occasion and never used it effectively when he did.
Strong claim for a penalty in the first half turned down. Didn't really link up with Messi as much as either would have liked. Was putting in crosses when ideally he should have been getting on the end of them.