PSG has now won the prestigious trophy on fourteen separate occasions.
The Parisian giants needed a stoppage-time leveler followed by a successful penalty shootout to get past their arch-rivals in the Gulf and secure a record-extending fourth consecutive Trophee des Champions victory.
The European champions appeared to be sailing towards a straightforward win in the match featuring the French league winners and the French Cup holders after Ousmane Dembele found the net in the opening stages.
Yet, the southern French side struck two times late to take a shock advantage. Initially, Mason Greenwood scored from the penalty spot, before the defender inadvertently directed the ball into his own net for an own goal.
In a breathtaking twist of fortune, the Portuguese striker snatched a vital leveler in the final moments to force the match into a deciding shootout. The Parisian shot-stopper Lucas Chevalier then emerged as the key figure, stopping crucial kicks from O'Riley and Traore.
In the shootout, Ramos, the midfielder, the full-back, and the young talent all scored with composure for Paris Saint-Germain to seal a 4-1 penalty win.
Now 14-time winners PSG, who met last season's Ligue 1 second-placed team Marseille after achieving a domestic double, have now won this competition for the twelfth time in the last 13 years.