The Parisian club has now won the prestigious cup on 14 separate times.
Paris Saint-Germain required a dramatic equaliser followed by a successful penalty shootout to get past their arch-rivals in the Gulf and secure a fourth straight French Super Cup victory.
The Champions League holders seemed to be sailing towards a straightforward triumph in the match between the Ligue 1 winners and the Coupe de France holders after the French winger found the net early on.
However, the southern French side struck twice late to seize a surprise advantage. Initially, the English forward converted from the penalty spot, before Willian Pacho inadvertently directed the ball into his own net for an own-goal.
In a breathtaking turn of events, the Portuguese striker grabbed a vital leveler in the final seconds to send the contest into a deciding shootout. The Parisian shot-stopper Chevalier then stood as the key figure, saving decisive kicks from O'Riley and Hamed Traore.
In the shootout, Goncalo Ramos, the midfielder, Nuno Mendes, and the young talent all converted with composure for PSG to complete a convincing penalty win.
Now 14-time champions PSG, who met last season's Ligue 1 second-placed team Olympique de Marseille after completing a league and cup double, have now won this competition for the twelfth time in the last 13 years.
