The Parisian club has now won the prestigious cup on 14 separate times.
Paris Saint-Germain required 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 victory.
The European champions appeared to be coasting towards a straightforward triumph in the match featuring the Ligue 1 winners and the Coupe de France holders after the French winger opened the scoring in the opening stages.
Yet, Marseille fired twice in the closing moments to take a surprise advantage. First, Mason Greenwood converted from the penalty spot, before the defender unfortunately directed the ball into his own net for an own goal.
In a remarkable twist of fortune, Goncalo Ramos snatched a crucial leveler in the dying seconds to send the match into a penalty shootout. The Parisian shot-stopper Chevalier then stood as the hero, saving decisive attempts from Matt O'Riley and Hamed Traore.
In the shootout, Ramos, Vitinha, Nuno Mendes, and Desire Doue all converted with composure for Paris Saint-Germain to complete a 4-1 penalty win.
Now 14-time champions PSG, who met last season's Ligue 1 second-placed team Marseille after achieving a league and cup double, have now won this trophy for the 12th time in the last thirteen years.
