The Parisian club has now won the season-opening trophy on 14 different occasions.
Paris Saint-Germain needed a stoppage-time equaliser followed by a perfect penalty shootout 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 straightforward win in the showdown between the Ligue 1 champions and the French Cup winners after the French winger opened the net early on.
However, Marseille struck twice in the closing moments to take a surprise advantage. Initially, Mason Greenwood converted from the penalty spot, before the defender unfortunately directed the ball into his own net for an own-goal.
In a remarkable turn of fortune, Goncalo Ramos grabbed a crucial equaliser in the final moments to force the match into a deciding shootout. PSG goalkeeper Chevalier then emerged as the hero, stopping crucial attempts from Matt O'Riley and Hamed Traore.
In the shootout, Ramos, Vitinha, Nuno Mendes, and Desire Doue all converted with composure for PSG to complete a convincing shootout win.
Now 14-time winners Paris Saint-Germain, who met last season's Ligue 1 second-placed team Olympique de Marseille after achieving a league and cup double, have now lifted this competition for the 12th time in the last thirteen seasons.
