PSG has now claimed the prestigious cup on 14 separate occasions.
The Parisian giants required a stoppage-time leveler followed by a perfect spot-kick decider to overcome Marseille in the Gulf and secure a fourth straight Trophee des Champions title.
The Champions League holders seemed to be coasting towards a straightforward win in the showdown featuring the French league champions and the French Cup holders after the French winger opened the net in the opening stages.
Yet, the southern French side struck twice in the closing moments to take a surprise advantage. Initially, the English forward converted 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, Goncalo Ramos grabbed a crucial equaliser in the final seconds to send the contest into a penalty shootout. PSG goalkeeper Lucas Chevalier then emerged as the key figure, saving crucial kicks from Matt O'Riley and Hamed Traore.
From the spot, Ramos, Vitinha, the full-back, and the young talent all scored with composure for PSG to complete a 4-1 penalty win.
The record champions PSG, who faced last season's Ligue 1 second-placed team Marseille after completing a domestic double, have now won this trophy for the twelfth time in the last 13 seasons.
