PSG has now claimed the season-opening cup on fourteen separate times.
Paris Saint-Germain required a stoppage-time equaliser followed by a successful penalty shootout to get past their arch-rivals in the Gulf and capture a record-extending fourth consecutive French Super Cup victory.
The Champions League holders seemed to be coasting towards a straightforward win in the showdown featuring the French league champions and the French Cup holders after the French winger opened the net in the opening stages.
However, the southern French side fired twice late to take a shock advantage. Initially, Mason Greenwood converted from the spot-kick, before the defender inadvertently turned the ball into his own net for an own goal.
In a breathtaking turn of fortune, Goncalo Ramos grabbed a crucial leveler in the final seconds to force the contest into a deciding shootout. PSG goalkeeper Chevalier then stood as the hero, stopping decisive kicks from O'Riley and Hamed Traore.
From the spot, Goncalo Ramos, the midfielder, Nuno Mendes, and Desire Doue all converted with composure for PSG to seal a convincing penalty win.
Now 14-time winners PSG, who met last season's Ligue 1 runners-up Marseille after achieving a domestic double, have now won this competition for the twelfth time in the last thirteen years.
