PSG has now won the season-opening cup on fourteen separate occasions.
The Parisian giants needed a dramatic leveler followed by a perfect penalty shootout to get past Marseille in the Gulf and secure a fourth straight French Super Cup victory.
The Champions League holders appeared to be coasting towards a comfortable win in the showdown between the Ligue 1 winners and the Coupe de France holders after Ousmane Dembele opened the net early on.
Yet, Marseille struck twice in the closing moments to take a surprise lead. First, Mason Greenwood scored from the spot-kick, before the defender unfortunately turned the ball into his own net for an own-goal.
In a breathtaking turn of fortune, the Portuguese striker snatched a crucial equaliser in the dying seconds to force the contest into a deciding shootout. PSG goalkeeper Lucas Chevalier then emerged as the key figure, saving crucial kicks from O'Riley and Hamed Traore.
From the spot, Ramos, Vitinha, the full-back, and Desire Doue all converted successfully for PSG to complete a convincing penalty win.
Now 14-time winners PSG, who met last season's Ligue 1 runners-up Olympique de Marseille after achieving a domestic double, have now won this trophy for the twelfth time in the past thirteen seasons.
