PSG has now won the season-opening trophy on 14 different times.
The Parisian giants needed a stoppage-time leveler followed by a successful spot-kick decider to get past Marseille in the Gulf and capture a fourth straight Trophee des Champions victory.
The European champions appeared to be sailing towards a comfortable triumph in the match featuring the French league winners and the Coupe de France winners after Ousmane Dembele opened the scoring early on.
Yet, the southern French side struck twice late to take a shock advantage. Initially, Mason Greenwood converted from the spot-kick, before Willian Pacho inadvertently turned the ball into his own net for an own-goal.
In a breathtaking twist of events, Goncalo Ramos grabbed a vital leveler in the dying seconds to send the contest into a penalty shootout. The Parisian shot-stopper Chevalier then stood as the key figure, stopping crucial attempts from Matt O'Riley and Traore.
From the spot, Ramos, the midfielder, Nuno Mendes, and the young talent all converted with composure for Paris Saint-Germain to seal a convincing penalty win.
The record winners Paris Saint-Germain, who faced last season's Ligue 1 second-placed team Olympique de Marseille after achieving a domestic double, have now won this trophy for the 12th time in the last 13 seasons.
