The Parisian club has now claimed the season-opening trophy on 14 separate times.
Paris Saint-Germain required a dramatic equaliser followed by a perfect spot-kick decider to overcome their arch-rivals in the Gulf and capture a record-extending fourth consecutive French Super Cup title.
The European champions appeared to be sailing towards a comfortable triumph in the showdown between the Ligue 1 champions and the French Cup winners after the French winger found the net early on.
However, the southern French side struck twice late to seize a shock advantage. First, Mason Greenwood scored from the penalty spot, before Willian Pacho inadvertently directed the ball into his own net for an own goal.
In a breathtaking twist of fortune, Goncalo Ramos grabbed a crucial equaliser in the final seconds to force 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 scored successfully for PSG to seal a 4-1 shootout win.
The record champions PSG, who faced last season's Ligue 1 runners-up Marseille after completing a domestic double, have now lifted this competition for the 12th time in the past 13 years.
