PSG has now claimed the prestigious trophy on 14 different occasions.
The Parisian giants needed a dramatic equaliser followed by a perfect spot-kick decider to overcome their arch-rivals in Kuwait and secure a fourth straight French Super Cup victory.
The European champions appeared to be sailing towards a comfortable triumph in the showdown between the Ligue 1 champions and the French Cup winners after Ousmane Dembele found the net in the opening stages.
Yet, Marseille struck two times in the closing moments to seize a shock lead. First, Mason Greenwood scored from the penalty spot, before Willian Pacho unfortunately turned the ball into his own net for an own goal.
In a breathtaking twist of fortune, Goncalo Ramos grabbed a vital leveler in the dying moments to force the contest into a deciding shootout. The Parisian shot-stopper Lucas Chevalier then emerged as the hero, stopping decisive attempts from O'Riley and Traore.
In the shootout, Goncalo Ramos, the midfielder, Nuno Mendes, and the young talent all scored successfully for Paris Saint-Germain to complete a 4-1 shootout victory.
Now 14-time champions Paris Saint-Germain, who met last season's Ligue 1 runners-up Marseille after completing a domestic double, have now lifted this trophy for the twelfth time in the last 13 years.