Ernesto Valverde's team predictably dominated the opening 30 minutes, but PSV looked risky on the counter-attack with Steven Bergwijn curling a shot just wide of Marc-Andre ter Stegen's goal and Hirving Lozano missing one from distance after a speedy run down the right flank.
On top of interest from Inter, the 23-year-old, also attracted interest from Barcelona and admitted he dreams of one day donning the famous blue and red jersey.
PSV Eindhoven, led by Mexico breakout star Hirving Lozano, beat Den Haag 7-0 on Saturday.
Gameday 1 marked the long-awaited return of proper Champions League soccer, and it nearly looked like Messi and Co. never left.
"It's the most important game of my career so far, a game against a great team, in a great stadium against really good players".
PSV coach Mark van Bommel, who played alongside Messi during his one season as a Barca player in 2005-06, says he still counts Messi as the world's best and added, should they win, his players can fight it out for the Argentine's shirt on Tuesday.
Barcelona's talisman is one of the best free-kick takers in the world, and he's delivered once again with an absolutely stunning strike against PSV.
Indeed, Van Bommel has ordered them not to request Messi's shirt during the game.
It did not take too long for Messi to reach 61 group-stage goals in the Champions League, though, and it all came through some good play from the direct Dembele to win a free kick for his side 25 yards from goal.
'That is part of being a professional, to always be concentrating.
Briefly teammates with Messi at Barcelona between 2005-06, Van Bommel didn't hold back in Monday's news conference. "I know they will ask him for the shirt, but they shouldn't do it at halftime".