PSG has now claimed the prestigious trophy on 14 separate times.
The Parisian giants required a dramatic leveler followed by a successful penalty shootout to overcome Marseille in Kuwait and secure a record-extending fourth consecutive Trophee des Champions title.
The Champions League holders seemed to be coasting towards a comfortable triumph in the showdown between the French league champions and the Coupe de France holders after the French winger opened the scoring early on.
However, Marseille fired twice in the closing moments to take a shock lead. Initially, Mason Greenwood scored from the spot-kick, before Willian Pacho unfortunately turned the ball into his own net for an own-goal.
In a remarkable twist of fortune, the Portuguese striker snatched a crucial leveler in the final moments to send the contest into a penalty shootout. The Parisian shot-stopper Lucas Chevalier then emerged as the hero, stopping decisive attempts from O'Riley and Hamed Traore.
From the spot, Ramos, the midfielder, the full-back, and Desire Doue all converted successfully for Paris Saint-Germain to complete a 4-1 penalty win.
Now 14-time champions Paris Saint-Germain, who met last season's Ligue 1 second-placed team Olympique de Marseille after achieving a league and cup double, have now won this trophy for the twelfth time in the last 13 years.
