The Parisian club has now won the season-opening cup on fourteen different times.
Paris Saint-Germain needed a dramatic leveler followed by a successful penalty shootout to overcome Marseille in Kuwait and secure a fourth straight Trophee des Champions title.
The European champions appeared to be sailing towards a straightforward triumph in the showdown between the Ligue 1 winners and the Coupe de France winners after Ousmane Dembele found the scoring in the opening stages.
Yet, the southern French side fired twice late to take a surprise lead. First, Mason Greenwood converted from the spot-kick, before Willian Pacho unfortunately turned the ball into his own net for an own-goal.
In a remarkable twist of events, Goncalo Ramos grabbed a crucial equaliser in the final seconds to force the match into a deciding shootout. PSG goalkeeper Lucas Chevalier then emerged as the key figure, saving decisive 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 4-1 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 13 seasons.