The Parisian club has now won the season-opening cup on fourteen different occasions.
Paris Saint-Germain needed a stoppage-time equaliser followed by a perfect penalty shootout to overcome their arch-rivals in Kuwait and secure a record-extending fourth consecutive Trophee des Champions victory.
The Champions League holders appeared to be sailing towards a straightforward triumph in the showdown between the Ligue 1 winners and the Coupe de France winners after Ousmane Dembele opened the scoring in the opening stages.
Yet, Marseille fired two times late to seize a shock advantage. Initially, Mason Greenwood scored from the spot-kick, before the defender inadvertently turned the ball into his own net for an own goal.
In a remarkable turn of fortune, the Portuguese striker grabbed a crucial leveler in the final seconds to send the contest into a deciding shootout. The Parisian shot-stopper Lucas Chevalier then stood as the key figure, stopping decisive kicks from O'Riley and Hamed Traore.
In the shootout, Ramos, Vitinha, the full-back, and Desire Doue all scored successfully for Paris Saint-Germain to complete a convincing shootout win.
The record winners PSG, who faced last season's Ligue 1 second-placed team Marseille after completing a league and cup double, have now won this competition for the twelfth time in the past thirteen seasons.