The Argentinean magician produced yet another masterclass as PSV Eindhoven became his 30th Champions League victim.
Barcelona also proved why the La Liga champions forked out £100million on Ousmane Dembele after he doubled their lead with a scintillating second.
But it was Messi who grabbed the headlines after bagging Champions League goal 104 and number 559 for his club.
PSV Eindhoven came into the contest on the back of seven straight wins but it wasn't long before they received a Messi sucker punch.
After Dembele was hacked down 25-yards out, Messi went for precision over power to curl in an inch perfect free-kick, leaving the keeper with no chance.
Barca, five-time winners of the competition, were far from their usual high standards in the early stages and came within inches of falling behind on 17 minutes.
PSV's Steven Bergwijn broke down the left, cut onto his right foot sent a stinging shot just wide of the far post.
It was the wake-up call that the huge favourites needed and the star-studded Catalan side started to carve out chances.
Luis Suarez spurned a chance from Messi's through ball and Phillipe Coutinho was denied from distance.
It was then time for the Messi show after Dembele was taken down following a blistering run at the defence.
His unstoppable free-kick put Barca in the driving seat and PSV's heads visibly dropped.
PSV's full-back did have a long-ranged effort from distance but the game was over when Dembele made it two.
His wonderful piece of skill beat two defenders before he curled in a beauty from distance.
The floodgates threatened to open and just two minutes later Messi latched onto Ivan Rakitic's chipped pass to fire low into the bottom corner.
And he wasn't quite done yet when Suarez combined with his close pal to leave Messi taking home yet another match ball.
It wasn't a perfect evening for Barca after Samuel Umtiti was sent off for a second yellow meaning he will miss the clash against Tottenham at Wembley.
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