The Parisian club has now claimed the season-opening cup on 14 different times.
The Parisian giants needed a stoppage-time leveler followed by a perfect spot-kick decider to overcome Marseille in Kuwait and secure a fourth straight Trophee des Champions title.
The Champions League holders seemed to be sailing towards a comfortable win in the match between the Ligue 1 champions and the Coupe de France holders after the French winger opened the scoring in the opening stages.
However, Marseille fired twice late to seize a surprise lead. Initially, the English forward converted from the penalty spot, before Willian Pacho inadvertently directed the ball into his own net for an own-goal.
In a remarkable twist of events, Goncalo Ramos snatched a vital leveler in the final moments to send the contest into a penalty shootout. PSG goalkeeper Chevalier then stood as the key figure, stopping decisive kicks from O'Riley and Traore.
From the spot, Ramos, Vitinha, Nuno Mendes, and Desire Doue all converted with composure for PSG to complete a 4-1 shootout victory.
The record champions PSG, who met last season's Ligue 1 second-placed team Marseille after achieving a domestic double, have now won this trophy for the 12th time in the past 13 seasons.
