PSG has now won the prestigious cup on fourteen separate occasions.
Paris Saint-Germain needed a stoppage-time equaliser followed by a successful spot-kick decider to get past their arch-rivals in the Gulf and capture a fourth straight Trophee des Champions victory.
The Champions League holders appeared to be sailing towards a straightforward win in the showdown featuring the French league champions and the Coupe de France winners after the French winger found the scoring early on.
However, Marseille fired twice late to seize a surprise lead. First, Mason Greenwood converted from the penalty spot, before Willian Pacho unfortunately turned the ball into his own net for an own goal.
In a breathtaking turn of events, the Portuguese striker snatched a vital leveler in the dying moments to send the match into a deciding shootout. PSG goalkeeper Chevalier then stood as the hero, saving crucial attempts from Matt O'Riley and Traore.
In the shootout, Goncalo Ramos, the midfielder, the full-back, and Desire Doue all converted successfully for PSG to seal a 4-1 shootout win.
The record champions Paris Saint-Germain, who faced last season's Ligue 1 second-placed team Marseille after completing a domestic double, have now won this trophy for the 12th time in the last 13 seasons.
