PSG has now secured the prestigious cup on fourteen different times.
Paris Saint-Germain required a stoppage-time equaliser followed by a perfect spot-kick decider to get past their arch-rivals in the Gulf and secure a record-extending fourth consecutive French Super Cup victory.
The European champions appeared to be sailing towards a straightforward triumph in the showdown between the French league winners and the French Cup holders after the French winger found the scoring early on.
Yet, the southern French side fired two times in the closing moments to take a surprise advantage. First, Mason Greenwood converted from the penalty spot, before the defender unfortunately turned the ball into his own net for an own goal.
In a remarkable twist of fortune, Goncalo Ramos grabbed a vital leveler in the dying seconds to force the contest into a deciding shootout. The Parisian shot-stopper Chevalier then emerged as the key figure, stopping crucial kicks from O'Riley and Traore.
From the spot, Goncalo Ramos, Vitinha, the full-back, and Desire Doue all converted with composure for Paris Saint-Germain to seal a convincing shootout win.
The record winners PSG, who met last season's Ligue 1 second-placed team Marseille after achieving a domestic double, have now won this trophy for the twelfth time in the last thirteen years.
