The Parisian club has now won the season-opening trophy on 14 separate times.
The Parisian giants required a stoppage-time equaliser followed by a perfect spot-kick decider to overcome Marseille in Kuwait and secure a fourth straight Trophee des Champions victory.
The European champions appeared to be coasting towards a straightforward triumph in the match featuring the Ligue 1 champions and the French Cup holders after Ousmane Dembele opened the net in the opening stages.
Yet, Marseille struck two times late 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 twist of fortune, the Portuguese striker snatched a vital leveler in the final seconds to force the match into a penalty shootout. The Parisian shot-stopper Lucas Chevalier then stood as the hero, stopping crucial kicks from O'Riley and Hamed Traore.
In the shootout, Ramos, Vitinha, Nuno Mendes, and Desire Doue all converted successfully for Paris Saint-Germain to seal a convincing shootout win.
The record champions PSG, who faced last season's Ligue 1 second-placed team Olympique de Marseille after achieving a domestic double, have now won this trophy for the 12th time in the past 13 seasons.