The Parisian club has now secured the season-opening cup on 14 separate times.
The Parisian giants needed a stoppage-time equaliser followed by a perfect penalty shootout to get past Marseille in the Gulf and capture a fourth straight Trophee des Champions title.
The Champions League holders seemed to be sailing towards a straightforward win in the match featuring the French league winners and the French Cup winners after Ousmane Dembele opened the scoring early on.
However, the southern French side fired twice in the closing moments to take a surprise lead. First, Mason Greenwood scored from the spot-kick, before Willian Pacho unfortunately directed the ball into his own net for an own-goal.
In a breathtaking twist of fortune, the Portuguese striker grabbed a crucial leveler in the final moments to send the contest into a penalty shootout. The Parisian shot-stopper Chevalier then stood as the hero, saving crucial kicks from O'Riley and Traore.
In the shootout, Ramos, Vitinha, Nuno Mendes, and Desire Doue all converted with composure for Paris Saint-Germain to complete a 4-1 shootout win.
Now 14-time champions Paris Saint-Germain, who faced last season's Ligue 1 second-placed team Marseille after completing a domestic double, have now lifted this competition for the twelfth time in the past thirteen years.
