PSG has now secured the season-opening trophy on fourteen separate times.
The Parisian giants needed a dramatic leveler followed by a successful spot-kick decider to get past Marseille in the Gulf and secure a fourth straight Trophee des Champions victory.
The Champions League holders appeared to be coasting towards a straightforward triumph in the showdown between the Ligue 1 winners and the Coupe de France holders after Ousmane Dembele found the scoring early on.
Yet, the southern French side struck twice in the closing moments to seize a shock advantage. First, Mason Greenwood scored from the spot-kick, before Willian Pacho inadvertently turned the ball into his own net for an own-goal.
In a remarkable twist of fortune, the Portuguese striker grabbed a crucial equaliser in the final moments to send the match into a deciding shootout. PSG goalkeeper Chevalier then emerged as the key figure, stopping crucial kicks from Matt O'Riley and Traore.
From the spot, Ramos, Vitinha, the full-back, and Desire Doue all converted successfully for Paris Saint-Germain to seal a convincing shootout win.
Now 14-time champions PSG, who met last season's Ligue 1 second-placed team Marseille after achieving a league and cup double, have now won this competition for the 12th time in the past thirteen seasons.
