The Parisian club has now won the season-opening cup on 14 different occasions.
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 record-extending fourth consecutive French Super Cup title.
The Champions League holders appeared to be sailing towards a comfortable win in the showdown featuring the Ligue 1 winners and the French Cup winners after the French winger opened the scoring in the opening stages.
However, the southern French side struck twice in the closing moments to take a surprise advantage. Initially, the English forward scored from the spot-kick, before Willian Pacho unfortunately turned the ball into his own net for an own-goal.
In a breathtaking twist of events, Goncalo Ramos grabbed a crucial leveler in the dying seconds to send the match into a deciding shootout. PSG goalkeeper Chevalier then emerged as the key figure, stopping decisive kicks from O'Riley and Hamed Traore.
From the spot, Ramos, Vitinha, the full-back, and Desire Doue all converted successfully for PSG to seal a 4-1 penalty victory.
The record champions PSG, who met last season's Ligue 1 second-placed team Marseille after completing a domestic double, have now won this competition for the 12th time in the last thirteen years.
