The Parisian club has now won the season-opening cup on fourteen separate occasions.
Paris Saint-Germain needed 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 title.
The Champions League holders appeared to be coasting towards a straightforward win in the showdown between the Ligue 1 champions and the Coupe de France holders after Ousmane Dembele found the net early on.
However, the southern French side fired two times in the closing moments to take a shock lead. First, the English forward scored from the spot-kick, before the defender unfortunately directed the ball into his own net for an own goal.
In a remarkable turn of fortune, Goncalo Ramos snatched a crucial equaliser in the dying moments to force the match into a deciding shootout. PSG goalkeeper Lucas Chevalier then emerged as the key figure, stopping crucial attempts from O'Riley and Hamed Traore.
From the spot, Goncalo Ramos, the midfielder, Nuno Mendes, and the young talent all scored with composure for Paris Saint-Germain to seal a 4-1 penalty victory.
Now 14-time winners PSG, who faced last season's Ligue 1 second-placed team Marseille after achieving a league and cup double, have now won this trophy for the twelfth time in the last 13 years.
