The Parisian club has now claimed the prestigious cup on fourteen different times.
Paris Saint-Germain required a stoppage-time equaliser followed by a successful penalty shootout to get past Marseille in Kuwait and capture a fourth straight Trophee des Champions victory.
The Champions League holders seemed to be coasting towards a straightforward win in the showdown featuring the Ligue 1 winners and the French Cup winners after Ousmane Dembele opened the scoring in the opening stages.
However, Marseille struck twice late 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 turn of events, Goncalo Ramos grabbed a crucial equaliser in the dying moments to force the match into a penalty shootout. PSG goalkeeper Chevalier then stood as the hero, stopping decisive attempts from O'Riley and Hamed Traore.
From the spot, Ramos, Vitinha, the full-back, and the young talent all converted with composure for Paris Saint-Germain to complete a convincing penalty win.
The record winners Paris Saint-Germain, who met last season's Ligue 1 second-placed team Olympique de Marseille after achieving a domestic double, have now lifted this trophy for the twelfth time in the last thirteen years.
