PSG has now claimed the season-opening cup on fourteen different times.
Paris Saint-Germain required a stoppage-time equaliser followed by a successful spot-kick decider 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 coasting towards a comfortable win in the match between the French league winners and the French Cup holders after the French winger found the net early on.
Yet, the southern French side fired two times in the closing moments to seize a shock advantage. Initially, the English forward converted from the penalty spot, before Willian Pacho unfortunately directed the ball into his own net for an own-goal.
In a remarkable twist of events, Goncalo Ramos snatched a vital equaliser in the dying moments to send the match into a penalty shootout. The Parisian shot-stopper Chevalier then emerged as the key figure, saving decisive kicks from O'Riley and Hamed Traore.
From the spot, Goncalo Ramos, Vitinha, Nuno Mendes, and the young talent all converted with composure for PSG to complete a 4-1 shootout victory.
The record winners PSG, who met last season's Ligue 1 second-placed team Marseille after achieving a league and cup double, have now won this competition for the twelfth time in the past 13 years.
