An entertaining friendly in the French capital saw the visitors pegged back after taking a two-goal lead, before the centre-back scored the decisive spot-kick to clinch victory
Rafinha opened the scoring early on, before two penalties - one for each side - were converted by Lionel Messi and Zlatan Ibrahimovic. Zoumana Camara netted late on to send the game to spot-kicks.
In the ensuing shootout, PSG missed both early kicks, with Barca racing into a 3-0 lead. Sylvain Armand reduced the deficit, but Gerard Pique netted to win it for the visitors.
After an energetic start from the Blaugrana in the French capital, it took only six minutes for the visitors to break the deadlock.
A speculative run from Alexis Sanchez on the flank saw the Chilean drill the ball into the box. Youngster Rafinha, who plies his trade with Barcelona B, benefited from a poor clearance by defender Alex, before latching on to the ball and firing past Nicholas Douchez.
Les Parisiens were noticeably lethargic in the early stages, and were unable to contain a Barcelona side famed for their continuous passing movements. Lionel Messi attempted an effort from distance, before having a shot easily saved by Douchez.
Carlo Ancelotti's side took time to slip into their rhythm in the French capital, though they did carve out a number of opportunities in the first half.
A move that originated from Javier Pastore saw a threatening ball whipped into the box from the right flank, though Ibrahimovic could not get the decisive touch on it.
Les Parisiens illustrated their increasing superiority in attack, but were almost undone on the counter-attack again. A lofted ball in the path of Messi saw the Argentine superstar dart in past Alex and unleash a shot, but it narrowly flew over Douchez's bar.
The second half brought the customary spate of substitutions, with Marco Verratti and Salvatore Sirigu among others making their PSG bows.
Seven minutes into the second period, however, and Barcelona were awarded a penalty. Mamadou Sakho was adjudged to have felled Sanchez in the box, with Messi stepping up to wrongfoot Sirigu and put the Blaugrana 2-0 ahead.
On the hour, PSG themselves were awarded a penalty by referee Said Ennijmi after Montoya had fouled Lavezzi in the box. Ibrahimovic coolly slotted past Pinto to reduce the deficit, and register his first goal at the Parc des Princes.
Substitutes Blaise Matuidi and Kevin Gameiro combined well late on, forcing Tito Vilanova's men into defensive mode. The hosts' perseverance paid off when Camara headed in from a brilliant delivery by Pastore late on, but they were thwarted by Barca goalkeeper Pinto in the shoot-out and it was the Catalans who claimed eventual victory.
The enthralling clash was perfect preparation for both sides, with PSG opening their Ligue 1 campaign against Lorient next Saturday, while the Catalans take on Real Madrid in the Spanish Supercopa on August 23.