The Parisian club has now secured the season-opening cup on 14 separate occasions.
Paris Saint-Germain needed a stoppage-time leveler followed by a perfect penalty shootout to get past their arch-rivals in the Gulf and capture a fourth straight French Super Cup title.
The European champions seemed to be sailing towards a straightforward win in the match between the French league winners and the French Cup winners after the French winger found the net in the opening stages.
However, the southern French side fired twice late to seize a shock advantage. First, Mason Greenwood scored from the penalty spot, before the defender inadvertently directed the ball into his own net for an own goal.
In a remarkable turn of events, the Portuguese striker snatched a crucial equaliser in the final seconds to force the contest into a penalty shootout. PSG goalkeeper Lucas Chevalier then emerged as the key figure, stopping decisive attempts from Matt O'Riley and Hamed Traore.
From the spot, Goncalo Ramos, the midfielder, Nuno Mendes, and the young talent all scored with composure for PSG to seal a 4-1 penalty win.
The record champions PSG, who faced last season's Ligue 1 second-placed team Marseille after completing a league and cup double, have now lifted this trophy for the twelfth time in the past 13 seasons.
