PSG has now claimed the prestigious trophy on 14 separate occasions.
Paris Saint-Germain required a stoppage-time leveler followed by a perfect spot-kick decider to overcome their arch-rivals in the Gulf and secure a record-extending fourth consecutive Trophee des Champions victory.
The Champions League holders seemed to be coasting towards a straightforward win in the showdown featuring the Ligue 1 champions and the French Cup winners after the French winger found the scoring early on.
However, the southern French side struck twice in the closing moments to take a shock lead. Initially, 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 twist of fortune, the Portuguese striker grabbed a vital equaliser in the dying seconds to send the contest into a penalty shootout. PSG goalkeeper Lucas Chevalier then stood as the hero, saving crucial kicks from O'Riley and Hamed Traore.
In the shootout, Ramos, Vitinha, the full-back, and Desire Doue all scored successfully for Paris Saint-Germain to complete a 4-1 penalty win.
The record champions PSG, who met last season's Ligue 1 second-placed team Marseille after completing a domestic double, have now lifted this trophy for the twelfth time in the past thirteen seasons.
