PSG has now won the prestigious cup on 14 different times.
The Parisian giants required a stoppage-time leveler followed by a successful spot-kick decider to get past Marseille in the Gulf and secure a record-extending fourth consecutive Trophee des Champions victory.
The European champions appeared to be sailing towards a straightforward triumph in the showdown featuring the French league winners and the Coupe de France winners after the French winger opened the net early on.
However, the southern French side struck two times late to take a shock advantage. Initially, the English forward 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 send the match into a deciding shootout. PSG goalkeeper Chevalier then emerged as the hero, saving crucial attempts from O'Riley and Traore.
In the shootout, Ramos, Vitinha, the full-back, and the young talent all scored with composure for PSG to seal a convincing shootout victory.
Now 14-time champions PSG, who met last season's Ligue 1 second-placed team Olympique de Marseille after achieving a league and cup double, have now won this competition for the twelfth time in the last thirteen years.
