The visitors, who had not conceded all season before arriving at Parc des Princes, fell behind when former Chelsea defender David Luiz scored.
Lionel Messi grabbed an equaliser but Marco Verratti nodded in PSG's second.
Blaise Matuidi poked in a third and although Neymar reduced the deficit, Barcelona could not find an equaliser.
They pressed in the closing stages but found the PSG defence, led by the impressive Luiz, hard to break down.

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