PSG has now won the season-opening trophy on fourteen different occasions.
The Parisian giants required a dramatic leveler followed by a perfect penalty shootout to get past Marseille in Kuwait and capture a fourth straight Trophee des Champions title.
The Champions League holders seemed to be sailing towards a comfortable win in the match featuring the Ligue 1 champions and the French Cup holders after Ousmane Dembele opened the scoring early on.
However, the southern French side fired two times in the closing moments to seize a shock lead. 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 breathtaking twist of fortune, the Portuguese striker grabbed a crucial equaliser in the final seconds to send the match into a penalty shootout. PSG goalkeeper Chevalier then emerged as the hero, stopping decisive attempts from O'Riley and Hamed Traore.
From the spot, Ramos, Vitinha, Nuno Mendes, and Desire Doue all scored successfully for Paris Saint-Germain to seal a convincing penalty win.
Now 14-time winners Paris Saint-Germain, who faced last season's Ligue 1 second-placed team Marseille after completing a domestic double, have now lifted this trophy for the twelfth time in the past 13 years.
