The French Champions have not been beaten at home in the Champions League since 2004 and their record continued in a five-goal thriller.
PSG took the lead on 11 minutes and it was Luiz – a player linked with a move to Barcelona before he finally left Chelsea for Paris in the summer – who got the goal. Dani Alves was penalized for handball and Lucas Moura’s free-kick dropped to Luiz who swept it past Marc-Andre ter Stegen.
Barcelona had made enquiries to sign Luiz in the past and made a more concerted effort to sign Marquinhos. They were facing both players and it was Luiz who had put paid to perfect defensive record.
Within a minute, however, the visitors were level.
The luminous yellow shirts charged forward and Messi and Andres Iniesta played a wall pass inside the area with the Argentine finishing past Salvatore Sirigu for his 68th Champions League goal.
Now only Real Madrid’s Raul has scored more and Messi had moved within three of the record. It was also Barcelona’s 500th goal in the European Cup.
Messi created Barca’s next real chance with a lofted pass that Neymar stretched to reach ahead of Sirigu - he got there first but failed to keep this shot down.
From so nearly taking the lead, Barcelona were soon behind again. Jordi Alba lost possession, PSG won a corner and from Thiago Motta’s kick Marco Verratti scored at the far post.
It a owed plenty to fine delivery, but even more to Ter Stegen wandering off his line and failing to claim the ball as it sailed over his head it, leaving the goal at Verratti’s mercy.
The old demons of not being able to defend set-pieces had undone Barcelona, with them conceding from a free-kick and a corner.
The game remained ridiculously open in what was left of the first half – something that suited Luiz. The Brazilian exists somewhere between total football and total chaos.
He had one run down the right wing, one run down the left wing, and there was some kamikaze defending, but he had scored one of the goals that sent his team down the tunnel leading 2-1 at half
The open spaces brought more goals at the start of the second half. PSG were doubling up on Alba with Lucas Moura and Gregory van der Wiel down the Barca left and the home side’s full back crossed from the right for Blaise Matuidi to score the third.
Barcelona repeated their first half trick of responding inside a minute with Alves’ cross was converted by Neymar to make it 3-2.
Barcelona were still looking exposed at the back and both Edinson Cavani and Javier Pastore had the chance to extend PSG’s lead.
A watching Zlatan Ibrahimovic didn’t know whether to smile or scowl as he watched the team attack so well without him.
Barca coach Luis Enrique brought on Xavi for his 143rd Champions League appearance, sending him past Raul’s competiton record, as Ivan Rakitic, who had also been at fault for PSG’s second goal, beaten in the air by Verratti, made way.
Barcelona’s best chance to salvage a point came with 15 minutes left when the ball dropped to Iniesta in space on the edge of the area. It was the same range he scored his most famous Champions League goal at Stamford Bridge in 2009. He even had the same colour shirt on but the shot was high and wide and the clock was now ticking down on Barcelona’s unbeaten start to the season.
There were still two more big chances with Alba shooting from inside the area only for Marquinhos to throw himself in front of the goalbound effort and Barcelona substitute Munir El Haddadi to hit the post from distance.
Marquinhos celebrated his block as if it were a goal, and PSG had their victory.
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