PSG has now won the season-opening cup on fourteen different times.
The Parisian giants required a dramatic leveler followed by a successful 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 champions and the French Cup holders after Ousmane Dembele found the scoring in the opening stages.
However, the southern French side fired two times late to take a surprise advantage. First, the English forward scored from the spot-kick, before the defender inadvertently directed the ball into his own net for an own-goal.
In a remarkable turn of fortune, Goncalo Ramos grabbed a crucial equaliser in the final moments to force the contest into a deciding shootout. PSG goalkeeper Lucas Chevalier then emerged as the hero, stopping crucial attempts from O'Riley and Traore.
From the spot, Goncalo Ramos, Vitinha, the full-back, and Desire Doue all scored with composure for Paris Saint-Germain to seal a convincing shootout victory.
The record champions PSG, who met last season's Ligue 1 runners-up Olympique de Marseille after achieving a domestic double, have now lifted this competition for the 12th time in the past 13 years.
