PSG has now won the season-opening cup on fourteen different occasions.
Paris Saint-Germain needed a dramatic leveler followed by a perfect penalty shootout to get past Marseille in the Gulf and capture a fourth straight Trophee des Champions title.
The European champions appeared to be sailing towards a straightforward triumph in the showdown between the French league champions and the Coupe de France holders after Ousmane Dembele found the scoring early on.
However, Marseille fired two times in the closing moments to seize a shock lead. Initially, Mason Greenwood converted from the spot-kick, before Willian Pacho inadvertently turned the ball into his own net for an own-goal.
In a breathtaking twist of fortune, Goncalo Ramos snatched a crucial leveler in the final seconds to force the contest into a penalty shootout. PSG goalkeeper Lucas Chevalier then emerged as the key figure, saving crucial attempts from O'Riley and Hamed 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 champions Paris Saint-Germain, who met last season's Ligue 1 runners-up Marseille after completing a league and cup double, have now won this trophy for the twelfth time in the past 13 seasons.