The Parisian club has now secured the season-opening cup on 14 different times.
Paris Saint-Germain needed a dramatic leveler followed by a perfect spot-kick decider to get past their arch-rivals in the Gulf and secure a fourth straight Trophee des Champions victory.
The European champions appeared to be coasting towards a comfortable triumph in the showdown featuring the Ligue 1 winners and the French Cup holders after the French winger opened the scoring in the opening stages.
Yet, the southern French side struck two times in the closing moments to seize a surprise advantage. First, the English forward scored from the spot-kick, before Willian Pacho unfortunately 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 moments to send the contest into a penalty shootout. The Parisian shot-stopper Chevalier then stood as the hero, saving decisive kicks from Matt O'Riley and Hamed Traore.
In the shootout, Goncalo Ramos, Vitinha, the full-back, and the young talent all converted successfully for PSG to seal a 4-1 penalty victory.
Now 14-time winners Paris Saint-Germain, who faced last season's Ligue 1 second-placed team Olympique de Marseille after completing a domestic double, have now won this competition for the 12th time in the past thirteen years.
