PSG has now claimed the season-opening cup on 14 different times.
The Parisian giants needed a stoppage-time leveler followed by a successful penalty shootout to overcome Marseille in the Gulf and capture a record-extending fourth consecutive Trophee des Champions victory.
The Champions League holders appeared to be sailing towards a straightforward win in the match between the French league champions and the Coupe de France holders after Ousmane Dembele found the net in the opening stages.
However, the southern French side fired twice late to seize a shock lead. Initially, the English forward scored from the penalty spot, before Willian Pacho inadvertently directed the ball into his own net for an own-goal.
In a breathtaking turn of fortune, the Portuguese striker snatched a vital equaliser in the final moments to force the contest into a deciding shootout. The Parisian shot-stopper Chevalier then stood as the key figure, stopping decisive kicks from O'Riley and Hamed Traore.
In the shootout, Goncalo Ramos, the midfielder, the full-back, and the young talent all converted with composure for PSG to complete a convincing penalty win.
Now 14-time champions Paris Saint-Germain, who met last season's Ligue 1 runners-up Marseille after achieving a domestic double, have now won this trophy for the twelfth time in the past 13 seasons.
