The Parisian club has now won the season-opening cup on 14 separate times.
The Parisian giants needed a stoppage-time equaliser 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 comfortable triumph in the showdown featuring the French league champions and the French Cup holders after Ousmane Dembele opened the scoring in the opening stages.
However, the southern French side fired two times late to take a surprise advantage. First, Mason Greenwood converted from the spot-kick, before the defender inadvertently turned the ball into his own net for an own goal.
In a breathtaking twist of fortune, Goncalo Ramos grabbed a crucial leveler in the dying seconds to send the match into a deciding shootout. PSG goalkeeper Chevalier then stood as the hero, stopping decisive attempts from O'Riley and Hamed Traore.
In the shootout, Ramos, the midfielder, the full-back, and the young talent all converted successfully for Paris Saint-Germain to complete a convincing shootout win.
Now 14-time champions PSG, who faced last season's Ligue 1 second-placed team Marseille after achieving a domestic double, have now lifted this competition for the twelfth time in the last 13 seasons.
