PSG has now claimed the prestigious cup on fourteen different occasions.
Paris Saint-Germain required a stoppage-time leveler followed by a successful spot-kick decider to overcome Marseille in the Gulf and secure a fourth straight French Super Cup title.
The European champions seemed to be sailing towards a straightforward win in the showdown featuring the French league champions and the Coupe de France holders after the French winger opened the net early on.
Yet, the southern French side struck twice late to seize a shock lead. Initially, Mason Greenwood converted from the penalty spot, before the defender inadvertently directed the ball into his own net for an own goal.
In a breathtaking twist of events, the Portuguese striker grabbed a crucial leveler in the dying seconds to force the match into a deciding shootout. PSG goalkeeper Lucas Chevalier then stood as the key figure, stopping crucial attempts from Matt O'Riley and Hamed Traore.
In the shootout, Ramos, the midfielder, the full-back, and the young talent all scored successfully for PSG to seal a convincing shootout win.
Now 14-time winners PSG, who met last season's Ligue 1 second-placed team Marseille after achieving a league and cup double, have now lifted this competition for the 12th time in the past thirteen seasons.