PSG has now claimed the prestigious cup on fourteen different times.
The Parisian giants needed a stoppage-time leveler followed by a perfect spot-kick decider to overcome their arch-rivals in the Gulf and capture a fourth straight Trophee des Champions victory.
The European champions seemed to be coasting towards a straightforward win in the showdown between the French league winners and the Coupe de France holders after Ousmane Dembele found the net early on.
However, the southern French side fired two times late to take a shock lead. First, the English forward converted from the spot-kick, before the defender inadvertently directed the ball into his own net for an own-goal.
In a breathtaking turn of fortune, the Portuguese striker grabbed a vital leveler in the dying moments to force the match into a penalty shootout. The Parisian shot-stopper Chevalier then emerged as the key figure, saving decisive kicks from O'Riley and Traore.
In the shootout, Goncalo Ramos, the midfielder, Nuno Mendes, and the young talent all converted with composure for Paris Saint-Germain to seal a convincing shootout win.
Now 14-time winners Paris Saint-Germain, who faced last season's Ligue 1 second-placed team Olympique de Marseille after completing a league and cup double, have now lifted this trophy for the 12th time in the last 13 seasons.
