The Catalans, who had not even conceded a goal all season in seven matches before this one, fell behind inside 10 minutes when David Luiz prodded in his first PSG goal.
Barcelona needed just two minutes to draw level thanks to a marvellous Lionel Messi strike, but Marco Verratti headed the hosts back in front after 26 minutes and Blaise Matuidi added another in the 54th minute.
Neymar reduced the deficit, yet Paris held on for their first win in the group after a 1-1 draw at Ajax two weeks ago, while Barca failed to build on a narrow 1-0 win over APOEL of Cyprus in their first outing.
Barcelona arrived in France in fine form but this was billed as their biggest test since the arrival of Luis Enrique as coach in the summer, even if their hosts were denied the services of Ezequiel Lavezzi and captain Thiago Silva as well as the prolific Ibrahimovic.
Edinson Cavani spearheaded their attack, while Barcelona again had Marc-Andre ter Stegen in goal in Europe rather than La Liga regular Claudio Bravo.
But their previously watertight defence looked rather fragile against a PSG side who started with all guns blazing and were soon rewarded.
Daniel Alves gave away a free-kick for stopping a Paris attack with his hand, and the home side opened the scoring from the resulting delivery, Luiz controlling Lucas’s ball in from the left before turning and poking the ball into the far corner from eight yards.
Barcelona’s defence had finally been breached for the first time this season after 640 minutes, but their response was immediate.
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