It was his second free kick goal in three home games this season.
Camp Nou gave Dembele the ovation he deserved. Both of which were quintessential goals from the Argentinian superstar, who now has scored more Champions League/European Cup hat tricks than any other player.
Messi scored the opener with a brilliant free-kick.
"Playing at Camp Nou is a dream of mine, and we'll have to deliver our best effort in order to try winning it. Barça being keen on me last summer?"
Messi and Cristiano Ronaldo have battled each other for years in the Champions League and the Barcelona icon has started his campaign off in the flawless possible manner, with Ronaldo waiting to make his first European appearance for Juventus against Valencia on Wednesday.
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He said: "There's not only Messi in this Barcelona".
However, just after the half-hour mark, PSV took too many players forward and Nick Viergever was forced to concede a foul just outside the box.
Messi's goals were his 101th, 102nd and 103rd in the Champions League, second only to former Real Madrid striker Cristiano Ronaldo all-time.
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A sublime finish from Dembele, which Zoet had no chance of getting to, gave the hosts some breathing space, and Messi then doubled his personal tally for the night by guiding Rakitic's lofted pass into the bottom corner with a first-time shot.
Naby Keita’s display for Liverpool against Tottenham showed room for improvement
Paris Saint-Germain captain Thiago Silva believes the world's two best attacks will meet when his team face Liverpool in the Champions League .
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