The Parisian club has now secured the prestigious trophy on 14 different occasions.
Paris Saint-Germain required a dramatic leveler followed by a successful spot-kick decider to get past Marseille in the Gulf and secure a record-extending fourth consecutive French Super Cup title.
The Champions League holders appeared to be sailing towards a straightforward triumph in the showdown featuring the Ligue 1 winners and the Coupe de France winners after Ousmane Dembele found the net in the opening stages.
Yet, the southern French side struck two times late to seize a shock lead. First, Mason Greenwood scored from the penalty spot, before the defender inadvertently directed the ball into his own net for an own-goal.
In a remarkable turn of fortune, Goncalo Ramos grabbed a crucial equaliser in the dying seconds to send the match into a penalty shootout. The Parisian shot-stopper Lucas Chevalier then stood as the hero, stopping decisive kicks from Matt O'Riley and Hamed Traore.
In the shootout, Ramos, Vitinha, Nuno Mendes, and the young talent all converted successfully for PSG to seal a 4-1 penalty victory.
The record winners PSG, who faced last season's Ligue 1 runners-up Olympique de Marseille after achieving a domestic double, have now won this competition for the twelfth time in the past 13 seasons.
