The Parisian club has now secured the season-opening cup on 14 different times.
Paris Saint-Germain needed a dramatic equaliser followed by a successful penalty shootout to get past Marseille in Kuwait and capture a record-extending fourth consecutive Trophee des Champions victory.
The Champions League holders seemed to be coasting towards a comfortable triumph in the match between the French league champions and the Coupe de France winners after Ousmane Dembele found the net early on.
However, Marseille struck two times in the closing moments to take a shock advantage. First, the English forward scored from the penalty spot, before Willian Pacho unfortunately turned the ball into his own net for an own goal.
In a remarkable turn of events, the Portuguese striker grabbed a vital leveler in the final moments to force the contest into a deciding shootout. PSG goalkeeper Chevalier then stood as the key figure, stopping decisive attempts from O'Riley and Hamed Traore.
In the shootout, Goncalo Ramos, the midfielder, the full-back, and Desire Doue all scored with composure for Paris Saint-Germain to complete a convincing shootout win.
Now 14-time champions Paris Saint-Germain, who met last season's Ligue 1 runners-up Olympique de Marseille after achieving a domestic double, have now lifted this trophy for the twelfth time in the last thirteen seasons.