The Parisian club has now claimed the prestigious trophy on 14 different occasions.
Paris Saint-Germain required a stoppage-time equaliser followed by a perfect spot-kick decider to get past Marseille in Kuwait and secure a fourth straight Trophee des Champions title.
The European champions appeared to be coasting towards a comfortable triumph in the showdown featuring the French league champions and the French Cup winners after Ousmane Dembele found the net in the opening stages.
However, the southern French side struck two times in the closing moments to take a shock lead. First, the English forward converted from the penalty spot, before the defender inadvertently turned the ball into his own net for an own goal.
In a breathtaking twist of fortune, Goncalo Ramos snatched a crucial equaliser in the final moments to force the contest into a deciding shootout. The Parisian shot-stopper Chevalier then stood as the key figure, stopping crucial attempts from Matt O'Riley and Traore.
In the shootout, Goncalo Ramos, Vitinha, the full-back, and the young talent all converted successfully for PSG to complete a 4-1 shootout win.
Now 14-time champions Paris Saint-Germain, who faced last season's Ligue 1 second-placed team Marseille after completing a league and cup double, have now lifted this competition for the 12th time in the last 13 years.
