PSG has now won the prestigious trophy on 14 separate times.
The Parisian giants needed a stoppage-time leveler followed by a perfect penalty shootout to overcome Marseille in the Gulf and capture a record-extending fourth consecutive French Super Cup title.
The Champions League holders seemed to be coasting towards a straightforward win in the match featuring the Ligue 1 winners and the French Cup holders after Ousmane Dembele found the scoring in the opening stages.
Yet, Marseille fired two times late to seize a shock lead. First, the English forward scored from the penalty spot, before the defender inadvertently directed the ball into his own net for an own-goal.
In a breathtaking turn of events, Goncalo Ramos snatched a vital equaliser in the dying seconds to force the contest into a deciding shootout. PSG goalkeeper Lucas Chevalier then stood as the hero, saving decisive attempts from O'Riley and Traore.
In the shootout, Ramos, Vitinha, Nuno Mendes, and Desire Doue all scored successfully for Paris Saint-Germain to seal a convincing penalty victory.
The record winners PSG, who faced last season's Ligue 1 second-placed team Marseille after achieving a domestic double, have now won this competition for the 12th time in the last 13 years.
