PSG has now claimed the prestigious cup on 14 separate times.
Paris Saint-Germain required a stoppage-time equaliser followed by a perfect spot-kick decider to overcome Marseille in the Gulf and capture a fourth straight French Super Cup title.
The European champions appeared to be sailing towards a comfortable win in the match between the French league champions and the Coupe de France winners after Ousmane Dembele found the scoring early on.
Yet, the southern French side struck two times in the closing moments to take a shock lead. Initially, the English forward converted from the penalty spot, before the defender unfortunately directed the ball into his own net for an own-goal.
In a breathtaking turn of fortune, Goncalo Ramos grabbed a vital leveler in the dying seconds to send the contest into a penalty shootout. The Parisian shot-stopper Lucas Chevalier then stood as the key figure, stopping decisive attempts from O'Riley and Hamed Traore.
In the shootout, Ramos, Vitinha, the full-back, and the young talent all scored successfully for PSG to seal a convincing shootout win.
Now 14-time champions PSG, who met last season's Ligue 1 second-placed team Olympique de Marseille after completing a league and cup double, have now lifted this trophy for the 12th time in the last 13 seasons.
