PSG has now claimed the season-opening cup on 14 separate occasions.
Paris Saint-Germain needed a stoppage-time equaliser followed by a successful penalty shootout to get past Marseille in the Gulf and capture a fourth straight Trophee des Champions victory.
The European champions appeared to be coasting towards a straightforward win in the match between the Ligue 1 champions and the French Cup winners after Ousmane Dembele found the scoring in the opening stages.
However, the southern French side fired twice late to take a shock lead. Initially, the English forward converted from the spot-kick, before the defender inadvertently directed the ball into his own net for an own goal.
In a remarkable turn of events, Goncalo Ramos snatched a crucial equaliser in the dying moments to send the match into a deciding shootout. The Parisian shot-stopper Chevalier then emerged as the key figure, saving decisive kicks from O'Riley and Hamed Traore.
In the shootout, Goncalo Ramos, the midfielder, Nuno Mendes, and the young talent all converted successfully for Paris Saint-Germain to seal a convincing shootout win.
Now 14-time winners PSG, who met last season's Ligue 1 second-placed team Marseille after completing a league and cup double, have now lifted this competition for the twelfth time in the past 13 seasons.
