The Parisian club has now won the prestigious cup on 14 separate times.
The Parisian giants required a dramatic leveler followed by a successful spot-kick decider to overcome Marseille in the Gulf and capture a record-extending fourth consecutive Trophee des Champions victory.
The European champions seemed to be sailing towards a straightforward win in the showdown featuring the Ligue 1 champions and the Coupe de France holders after the French winger opened the net early on.
Yet, the southern French side struck twice late to take a surprise advantage. Initially, Mason Greenwood converted from the penalty spot, before Willian Pacho unfortunately directed the ball into his own net for an own-goal.
In a remarkable twist of events, the Portuguese striker grabbed a vital leveler in the final moments to send the contest into a deciding shootout. PSG goalkeeper Chevalier then emerged as the hero, stopping crucial kicks from Matt O'Riley and Traore.
From the spot, Goncalo Ramos, Vitinha, Nuno Mendes, and the young talent all converted successfully for PSG to seal a convincing penalty win.
Now 14-time champions Paris Saint-Germain, who met last season's Ligue 1 second-placed team Olympique de Marseille after completing a domestic double, have now lifted this competition for the twelfth time in the last thirteen seasons.
