PSG has now secured the season-opening cup on 14 separate occasions.
Paris Saint-Germain required a dramatic leveler followed by a successful penalty shootout to get past their arch-rivals in the Gulf and capture a fourth straight French Super Cup title.
The Champions League holders seemed to be coasting towards a straightforward triumph in the showdown featuring the Ligue 1 champions and the French Cup winners after Ousmane Dembele found the scoring in the opening stages.
However, Marseille struck twice late to take a shock advantage. First, Mason Greenwood converted from the penalty spot, before the defender inadvertently directed the ball into his own net for an own-goal.
In a breathtaking turn of fortune, the Portuguese striker snatched a vital leveler in the dying seconds to force the contest into a deciding shootout. The Parisian shot-stopper Lucas Chevalier then stood as the key figure, stopping decisive kicks from Matt O'Riley and Hamed Traore.
From the spot, Ramos, Vitinha, the full-back, and the young talent all converted with composure for PSG to seal a convincing penalty win.
The record champions PSG, who faced last season's Ligue 1 runners-up Marseille after achieving a domestic double, have now won this trophy for the twelfth time in the last thirteen seasons.
