PSG has now won the prestigious cup on fourteen different times.
The Parisian giants required a stoppage-time equaliser followed by a perfect spot-kick decider to overcome Marseille in Kuwait and capture a fourth straight French Super Cup title.
The Champions League holders appeared to be sailing towards a straightforward triumph in the match between the Ligue 1 champions and the Coupe de France winners after the French winger opened the net early on.
However, the southern French side fired twice late to take a surprise lead. First, Mason Greenwood converted from the penalty spot, before the defender unfortunately directed the ball into his own net for an own goal.
In a remarkable turn of events, the Portuguese striker snatched a crucial leveler in the final seconds to force the match into a deciding shootout. PSG goalkeeper Chevalier then emerged as the hero, saving decisive kicks from Matt O'Riley and Hamed Traore.
In the shootout, Ramos, the midfielder, Nuno Mendes, and the young talent all converted successfully for PSG to seal a convincing shootout win.
Now 14-time winners Paris Saint-Germain, who faced last season's Ligue 1 runners-up Marseille after completing a league and cup double, have now won this trophy for the 12th time in the past thirteen seasons.
