PSG has now secured the season-opening cup on 14 separate times.
The Parisian giants needed a stoppage-time leveler followed by a successful spot-kick decider to get past Marseille in the Gulf and secure a fourth straight Trophee des Champions title.
The European champions appeared to be sailing towards a comfortable triumph in the showdown featuring the Ligue 1 champions and the French Cup holders after Ousmane Dembele opened the net in the opening stages.
However, the southern French side fired two times late to seize a shock lead. Initially, the English forward scored from the spot-kick, before the defender inadvertently directed the ball into his own net for an own goal.
In a breathtaking twist of fortune, Goncalo Ramos grabbed a vital leveler in the dying moments to send the contest into a deciding shootout. The Parisian shot-stopper Chevalier then stood as the hero, stopping decisive attempts from Matt O'Riley and Traore.
From the spot, Ramos, the midfielder, the full-back, and the young talent all scored with composure for Paris Saint-Germain to complete a 4-1 shootout victory.
Now 14-time winners PSG, who faced last season's Ligue 1 runners-up Marseille after achieving a league and cup double, have now won this competition for the 12th time in the past thirteen seasons.
