The Parisian club has now secured the season-opening trophy on 14 different occasions.
Paris Saint-Germain needed a dramatic equaliser followed by a successful penalty shootout to overcome their arch-rivals in the Gulf and secure a record-extending fourth consecutive Trophee des Champions title.
The Champions League holders appeared to be sailing towards a straightforward triumph in the showdown featuring the French league champions and the French Cup winners after Ousmane Dembele found the net early on.
However, the southern French side fired twice late to seize a surprise lead. Initially, the English forward converted from the penalty spot, before the defender inadvertently directed the ball into his own net for an own goal.
In a breathtaking turn of events, the Portuguese striker grabbed a vital leveler in the final seconds to send the contest into a penalty shootout. The Parisian shot-stopper Chevalier then emerged as the key figure, stopping crucial attempts from O'Riley and Traore.
From the spot, Ramos, the midfielder, the full-back, and the young talent all scored with composure for Paris Saint-Germain to complete a 4-1 penalty victory.
Now 14-time champions PSG, who faced last season's Ligue 1 second-placed team Marseille after completing a domestic double, have now lifted this trophy for the 12th time in the last 13 seasons.
