The Parisian club has now won the prestigious cup on 14 separate times.
The Parisian giants needed a stoppage-time equaliser followed by a perfect spot-kick decider to overcome their arch-rivals in the Gulf and capture a record-extending fourth consecutive French Super Cup victory.
The Champions League holders seemed to be coasting towards a straightforward win in the match between the French league champions and the French Cup holders after the French winger found the scoring early on.
However, the southern French side fired twice in the closing moments to seize a surprise lead. Initially, the English forward converted from the spot-kick, before the defender inadvertently directed the ball into his own net for an own goal.
In a remarkable twist of fortune, Goncalo Ramos snatched a crucial leveler in the final seconds to send the match into a penalty shootout. PSG goalkeeper Lucas Chevalier then stood as the key figure, stopping crucial kicks from O'Riley and Hamed Traore.
From the spot, Goncalo Ramos, Vitinha, the full-back, and Desire Doue all converted successfully for Paris Saint-Germain to seal a 4-1 shootout victory.
Now 14-time champions Paris Saint-Germain, who met last season's Ligue 1 runners-up Olympique de Marseille after achieving a domestic double, have now won this trophy for the twelfth time in the past 13 years.
