PSG has now secured the season-opening trophy on fourteen separate occasions.
The Parisian giants required a stoppage-time leveler followed by a successful penalty shootout to overcome Marseille in the Gulf and capture a record-extending fourth consecutive French Super Cup victory.
The European champions appeared to be sailing towards a straightforward triumph in the showdown featuring the French league winners and the French Cup winners after Ousmane Dembele found the scoring in the opening stages.
Yet, Marseille struck two times late to seize a surprise lead. First, the English forward scored 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 grabbed a crucial equaliser in the dying moments to force the contest into a deciding shootout. The Parisian shot-stopper Lucas Chevalier then stood as the hero, saving decisive kicks from O'Riley and Traore.
From the spot, Ramos, Vitinha, the full-back, and Desire Doue all scored with composure for Paris Saint-Germain to complete a convincing shootout victory.
The record winners PSG, who faced last season's Ligue 1 second-placed team Marseille after completing a domestic double, have now won this competition for the twelfth time in the past thirteen years.