PSG has now secured the prestigious trophy on 14 different occasions.
Paris Saint-Germain required a stoppage-time equaliser followed by a successful spot-kick decider to get past Marseille in the Gulf and secure a fourth straight Trophee des Champions victory.
The European champions appeared to be sailing towards a comfortable triumph in the match 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 two times late to take a surprise advantage. Initially, the English forward scored from the penalty spot, before Willian Pacho unfortunately directed the ball into his own net for an own goal.
In a remarkable turn of fortune, the Portuguese striker snatched a vital equaliser in the dying moments to force the contest into a penalty shootout. PSG goalkeeper Chevalier then emerged as the hero, stopping decisive attempts from O'Riley and Hamed Traore.
From the spot, Goncalo Ramos, Vitinha, Nuno Mendes, and Desire Doue all converted with composure for Paris Saint-Germain to complete a convincing shootout victory.
The record champions PSG, who faced last season's Ligue 1 second-placed team Olympique de Marseille after achieving a domestic double, have now lifted this trophy for the 12th time in the last 13 seasons.
