João Neves opened the scoring in the ninth minute, with Désiré Doué and Senny Mayulu adding further goals in the 12th and 13th minutes. Fabián Ruiz made it four before the 20-minute mark, then scored again five minutes after half-time. Substitute David Boly completed the rout in the 78th minute.
Villarreal coach Iñigo Pérez was left to reflect on a damaging opening spell that effectively ended the contest before his team could recover.
“We're in a bad way. We've conceded the goals so close together and the blow was insurmountable. We weren't even able to get close to them,” he said.
Pérez also refused to make his own future the focus after the defeat, insisting his priority was finding a way to improve the team.
“What hurts me is not being able to respond to the trust placed in me and give my players the tools to get results,” he said. “It causes me pain to think about the people who come to watch and how they go home.”
Asked about the possibility of being dismissed, he added: “The future of Iñigo is not important. I don't stop to think about that. The only thing I'm looking for is solutions to turn the situation around.”
The coach also accepted responsibility for the performance, rather than placing the blame on his players.
“When you lose 6-0, the only thing you can do is look at how you've set up the match and improve,” he said. “We've all seen that the mistakes happen constantly and we have to accept that. We have to go back to the source, and perhaps I haven't trained it well enough.”
Luis Enrique, meanwhile, expressed discomfort at the scale of the victory, despite praising his team's approach and intensity.
“I don't like this type of result, but we try to respect the opponent by playing in the same way all the time,” the PSG coach said.
He felt Villarreal had found the early deficit particularly difficult to overcome.
“After 0-3, there is no team that can withstand that, because you can change the match but it's difficult for opponents to overcome that result,” he said.
Luis Enrique added that PSG's approach would not change simply because they had built a commanding lead.
“It's our way of respecting the opponent, playing with the same intensity all the time,” he said, while acknowledging that the circumstances had made the evening especially difficult for Villarreal.