PSG has now won the prestigious trophy on 14 separate occasions.
Paris Saint-Germain needed a stoppage-time leveler followed by a perfect spot-kick decider to get past their arch-rivals in the Gulf and capture a fourth straight French Super Cup victory.
The Champions League holders seemed to be sailing towards a comfortable triumph in the match between the French league winners and the French Cup winners after the French winger opened the scoring in the opening stages.
However, the southern French side fired twice in the closing moments to seize a shock advantage. First, Mason Greenwood scored from the spot-kick, before the defender unfortunately directed the ball into his own net for an own goal.
In a breathtaking turn of events, Goncalo Ramos snatched a vital equaliser in the final moments to send the match into a deciding shootout. PSG goalkeeper Chevalier then emerged as the key figure, saving decisive attempts from O'Riley and Hamed Traore.
In the shootout, Ramos, Vitinha, Nuno Mendes, and Desire Doue all scored successfully for Paris Saint-Germain to seal a convincing penalty victory.
Now 14-time winners 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 trophy for the 12th time in the last 13 years.
