PSG has now won the season-opening cup on fourteen separate times.
The Parisian giants needed a dramatic equaliser followed by a successful penalty shootout to overcome their arch-rivals in the Gulf and secure a fourth straight 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 French Cup winners after Ousmane Dembele found the net in the opening stages.
However, Marseille struck two times late to seize a surprise lead. Initially, the English forward converted from the spot-kick, before the defender inadvertently turned the ball into his own net for an own goal.
In a remarkable turn of events, the Portuguese striker snatched a vital equaliser in the final seconds to send the match into a deciding shootout. PSG goalkeeper Chevalier then emerged as the hero, saving decisive kicks from O'Riley and Traore.
In the shootout, Ramos, Vitinha, the full-back, and the young talent all scored with composure for Paris Saint-Germain to seal a 4-1 penalty win.
Now 14-time champions PSG, who met last season's Ligue 1 second-placed team Marseille after completing a domestic double, have now won this trophy for the twelfth time in the past thirteen seasons.
