PSG has now won the prestigious cup on fourteen different times.
The Parisian giants needed a stoppage-time equaliser followed by a perfect spot-kick decider to get past Marseille in the Gulf and secure a fourth straight Trophee des Champions title.
The Champions League holders seemed to be coasting towards a comfortable triumph in the match featuring the Ligue 1 winners and the French Cup holders after Ousmane Dembele opened the scoring in the opening stages.
However, Marseille fired two times in the closing moments to seize a surprise lead. First, Mason Greenwood converted from the spot-kick, before Willian Pacho inadvertently directed the ball into his own net for an own-goal.
In a remarkable twist of fortune, the Portuguese striker grabbed a vital leveler in the final seconds to send the match into a deciding shootout. PSG goalkeeper Chevalier then emerged as the hero, stopping crucial attempts from O'Riley and Traore.
From the spot, Ramos, Vitinha, the full-back, and Desire Doue all converted with composure for Paris Saint-Germain to seal a convincing penalty win.
Now 14-time champions PSG, who faced last season's Ligue 1 second-placed team Marseille after achieving a domestic double, have now lifted this competition for the 12th time in the past thirteen seasons.
