PSG has now claimed the prestigious trophy on fourteen different occasions.
Paris Saint-Germain required a stoppage-time equaliser followed by a perfect penalty shootout to get past their arch-rivals in the Gulf and capture a record-extending fourth consecutive Trophee des Champions title.
The Champions League holders appeared to be sailing towards a comfortable win in the match between the French league champions and the Coupe de France holders after Ousmane Dembele found the scoring early on.
However, the southern French side fired two times late to take a shock lead. First, the English forward scored from the spot-kick, before Willian Pacho inadvertently turned the ball into his own net for an own-goal.
In a breathtaking turn of fortune, the Portuguese striker snatched a crucial equaliser in the final moments to send the contest into a deciding shootout. The Parisian shot-stopper Lucas Chevalier then emerged as the key figure, stopping decisive attempts from O'Riley and Traore.
In the shootout, Ramos, the midfielder, Nuno Mendes, and Desire Doue all scored successfully for Paris Saint-Germain to seal a 4-1 penalty victory.
The record champions PSG, who faced last season's Ligue 1 runners-up Marseille after completing a league and cup double, have now won this competition for the twelfth time in the last 13 years.
