The Parisian club has now secured the season-opening trophy on fourteen separate occasions.
Paris Saint-Germain needed a dramatic leveler followed by a perfect spot-kick decider to overcome their arch-rivals in the Gulf and capture a fourth straight French Super Cup victory.
The Champions League holders appeared to be sailing towards a straightforward win in the showdown featuring the French league champions and the Coupe de France winners after Ousmane Dembele opened the scoring in the opening stages.
Yet, the southern French side struck twice in the closing moments to seize a shock advantage. First, the English forward converted from the penalty spot, before the defender unfortunately turned the ball into his own net for an own goal.
In a remarkable twist of fortune, the Portuguese striker snatched a crucial leveler in the dying moments to send the contest into a penalty shootout. PSG goalkeeper Lucas Chevalier then stood as the key figure, saving decisive attempts from O'Riley and Traore.
From the spot, Goncalo Ramos, the midfielder, the full-back, and the young talent all converted with composure for PSG to seal a 4-1 shootout victory.
Now 14-time winners Paris Saint-Germain, who met last season's Ligue 1 second-placed team Olympique de Marseille after achieving a league and cup double, have now won this trophy for the twelfth time in the past 13 seasons.