A cool finish from Neymar and two superb solo goals from Luis Suarez won the game for the Spanish side.
Lionel Messi also hit the post with a curling shot from the edge of the box.
PSG struggled in the absence of suspended striker Zlatan Ibrahimovic but have hope thanks to Jeremy Mathieu's own goal.
Before the French defender's unfortunate contribution - which saw him deflect a 20-yard Gregory van der Wiel drive past his own keeper - it had been a disastrous game for PSG, who also lost captain Thiago Silva to injury.
The 30-year-old Brazilian limped off soon after his compatriot Neymar had opened the scoring for the visitors on a night of misery for the French side, who have now lost their unbeaten home record this season and suffered a first European defeat at the Parc des Princes in 34 matches.
In addition, they also lost top spot in Ligue 1 as Lyon beat Bastia 2-0 on Wednesday to usurp them in the table.
Barca's win was not without cost as they also suffered an injury blow of their own in the second half when Andres Iniesta left on a stretcher holding his lower back, although after the game manager Luis Enrique revealed that the midfielder had not suffered serious damage.
This game is the third of what will be ultimately be a four-match Champions League contest between these two sides this season, following on from two closely contested Group F encounters that both went in favour of the home side.
PSG were also without Ibrahimovic when they recorded a 3-2 win over the Catalan club in late September but there was to be no repeat of that famous victory against a confident and composed Barca side, who are now 11 matches unbeaten in all competitions and chasing the treble.
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