The Parisian club has now secured the prestigious trophy on 14 separate times.
Paris Saint-Germain required a stoppage-time leveler followed by a successful penalty shootout to overcome Marseille in the Gulf and capture a record-extending fourth consecutive Trophee des Champions title.
The European champions seemed to be coasting towards a comfortable win in the showdown between the French league champions and the Coupe de France holders after the French winger found the scoring in the opening stages.
However, Marseille fired twice late to seize a surprise advantage. First, the English forward converted from the spot-kick, before Willian Pacho inadvertently directed the ball into his own net for an own goal.
In a breathtaking twist of events, Goncalo Ramos grabbed a vital leveler in the dying moments to send the match into a penalty shootout. The Parisian shot-stopper Lucas Chevalier then emerged as the hero, stopping crucial kicks from O'Riley and Traore.
In the shootout, Goncalo Ramos, Vitinha, the full-back, and Desire Doue all converted successfully for Paris Saint-Germain to complete a 4-1 shootout win.
Now 14-time winners PSG, who met last season's Ligue 1 second-placed team Olympique de Marseille after completing a domestic double, have now lifted this competition for the 12th time in the past thirteen seasons.
