The Parisian club has now claimed the prestigious trophy on fourteen separate times.
Paris Saint-Germain required a dramatic leveler followed by a perfect spot-kick decider to get past Marseille in Kuwait and capture a fourth straight Trophee des Champions victory.
The European champions seemed to be coasting towards a comfortable triumph in the showdown featuring the French league champions and the French Cup holders after Ousmane Dembele opened the net early on.
Yet, the southern French side fired twice in the closing moments to take a surprise lead. Initially, Mason Greenwood converted from the penalty spot, before the defender inadvertently directed the ball into his own net for an own goal.
In a breathtaking twist of events, the Portuguese striker snatched a crucial equaliser in the dying moments to send the match into a penalty shootout. The Parisian shot-stopper Lucas Chevalier then stood as the key figure, saving crucial kicks from O'Riley and Traore.
From the spot, Goncalo Ramos, Vitinha, the full-back, and the young talent all scored successfully for Paris Saint-Germain to complete a convincing penalty win.
The record champions Paris Saint-Germain, who met last season's Ligue 1 second-placed team Olympique de Marseille after completing a league and cup double, have now won this competition for the 12th time in the past thirteen seasons.