PSG has now claimed the prestigious trophy on fourteen different times.
Paris Saint-Germain required a stoppage-time equaliser followed by a successful spot-kick decider to overcome Marseille in the Gulf and secure a fourth straight Trophee des Champions title.
The Champions League holders appeared to be coasting towards a straightforward triumph in the showdown featuring the French league winners and the Coupe de France winners after Ousmane Dembele found the net in the opening stages.
However, the southern French side struck twice late to seize a surprise advantage. Initially, the English forward scored from the penalty spot, before Willian Pacho unfortunately directed the ball into his own net for an own goal.
In a breathtaking twist of events, the Portuguese striker grabbed a crucial leveler in the final moments to force the contest into a deciding shootout. PSG goalkeeper Lucas Chevalier then stood as the key figure, stopping crucial kicks from Matt O'Riley and Traore.
In the shootout, Ramos, Vitinha, Nuno Mendes, and the young talent all converted successfully for Paris Saint-Germain to seal a 4-1 penalty victory.
Now 14-time winners PSG, who faced last season's Ligue 1 runners-up Marseille after achieving a league and cup double, have now won this trophy for the twelfth time in the last thirteen years.
