PSG has now claimed the prestigious cup on fourteen separate occasions.
The Parisian giants needed a stoppage-time equaliser followed by a successful spot-kick decider to overcome Marseille in the Gulf and capture a fourth straight French Super Cup victory.
The European champions seemed to be sailing towards a comfortable win in the showdown featuring the French league winners and the Coupe de France winners after the French winger found the scoring early on.
However, the southern French side struck twice in the closing moments to seize a surprise advantage. First, Mason Greenwood converted from the penalty spot, before the defender inadvertently turned the ball into his own net for an own-goal.
In a remarkable twist of events, the Portuguese striker snatched a crucial equaliser in the dying seconds to send the match into a deciding shootout. The Parisian shot-stopper Lucas Chevalier then emerged as the key figure, saving crucial kicks from O'Riley and Traore.
From the spot, Ramos, the midfielder, the full-back, and the young talent all scored with composure for PSG to seal a 4-1 penalty win.
Now 14-time winners Paris Saint-Germain, who faced last season's Ligue 1 second-placed team Olympique de Marseille after completing a domestic double, have now won this competition for the 12th time in the past thirteen years.