PSG has now won the season-opening trophy on fourteen different occasions.
The Parisian giants needed a dramatic leveler followed by a perfect spot-kick decider to overcome Marseille in the Gulf and capture a fourth straight French Super Cup title.
The Champions League holders appeared to be coasting towards a straightforward win in the showdown between the French league winners and the Coupe de France winners after Ousmane Dembele opened the net in the opening stages.
Yet, the southern French side fired two times late to take a shock lead. First, the English forward scored from the penalty spot, before Willian Pacho inadvertently turned the ball into his own net for an own goal.
In a remarkable turn of events, Goncalo Ramos snatched a crucial equaliser in the dying seconds to force the contest into a deciding shootout. PSG goalkeeper Lucas Chevalier then stood as the hero, stopping decisive attempts from O'Riley and Hamed Traore.
From the spot, Ramos, Vitinha, Nuno Mendes, and Desire Doue all converted with composure for Paris Saint-Germain to seal a convincing penalty win.
The record champions PSG, who met last season's Ligue 1 runners-up Marseille after completing a league and cup double, have now lifted this competition for the 12th time in the past 13 seasons.
