PSG has now secured the prestigious trophy on 14 separate times.
Paris Saint-Germain needed a stoppage-time leveler followed by a perfect spot-kick decider to overcome Marseille in the Gulf and secure a record-extending fourth consecutive Trophee des Champions title.
The European champions seemed to be coasting towards a comfortable triumph in the showdown featuring the French league winners and the French Cup winners after the French winger found the net in the opening stages.
Yet, Marseille fired two times late to seize a shock advantage. Initially, the English forward converted 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, Goncalo Ramos snatched a crucial equaliser in the final moments to force the contest into a deciding shootout. PSG goalkeeper Lucas Chevalier then emerged as the key figure, stopping crucial kicks from O'Riley and Traore.
From the spot, Goncalo Ramos, Vitinha, Nuno Mendes, and Desire Doue all converted successfully for PSG to complete a convincing penalty victory.
Now 14-time winners Paris Saint-Germain, who met last season's Ligue 1 runners-up Marseille after achieving a league and cup double, have now won this trophy for the 12th time in the past thirteen years.