The Parisian club has now secured the season-opening cup on 14 separate occasions.
The Parisian giants required a dramatic leveler followed by a successful spot-kick decider to overcome Marseille in the Gulf and secure a fourth straight Trophee des Champions title.
The European champions seemed to be sailing towards a straightforward win in the match featuring the French league champions and the Coupe de France winners after Ousmane Dembele opened the scoring in the opening stages.
However, the southern French side fired two times in the closing moments to take a shock lead. First, the English forward converted from the penalty spot, before the defender unfortunately directed the ball into his own net for an own-goal.
In a breathtaking turn of events, Goncalo Ramos grabbed a vital leveler in the dying seconds to send the match into a penalty shootout. The Parisian shot-stopper Chevalier then emerged as the hero, stopping decisive kicks from O'Riley and Traore.
From the spot, Ramos, the midfielder, the full-back, and Desire Doue all scored successfully for Paris Saint-Germain to seal a 4-1 shootout win.
The record winners Paris Saint-Germain, who faced last season's Ligue 1 runners-up Olympique de Marseille after completing a league and cup double, have now won this trophy for the 12th time in the past thirteen years.
