The Parisian club has now won the prestigious cup on 14 different times.
Paris Saint-Germain required a stoppage-time leveler followed by a perfect spot-kick decider to overcome Marseille in the Gulf and secure a fourth straight Trophee des Champions victory.
The Champions League holders appeared to be sailing towards a straightforward triumph in the showdown between the Ligue 1 champions and the Coupe de France winners after the French winger found the scoring early on.
Yet, Marseille struck twice late to seize a shock lead. Initially, the English forward scored from the spot-kick, before Willian Pacho unfortunately turned the ball into his own net for an own goal.
In a breathtaking turn of fortune, Goncalo Ramos grabbed a vital leveler in the final moments to send the contest into a penalty shootout. The Parisian shot-stopper Chevalier then emerged as the key figure, saving crucial kicks from O'Riley and Traore.
In the shootout, Goncalo Ramos, the midfielder, the full-back, and the young talent all scored with composure for PSG to complete a convincing penalty win.
The record champions PSG, who met last season's Ligue 1 runners-up Marseille after achieving a domestic double, have now lifted this competition for the 12th time in the past thirteen years.