PSG has now claimed the season-opening trophy on 14 separate times.
Paris Saint-Germain needed a stoppage-time equaliser followed by a successful penalty shootout to get past their arch-rivals in the Gulf and capture a record-extending fourth consecutive French Super Cup title.
The Champions League holders seemed to be coasting towards a comfortable triumph in the showdown between the Ligue 1 champions and the French Cup winners after the French winger found the scoring in the opening stages.
However, the southern French side struck two times late to seize a surprise lead. First, the English forward converted from the spot-kick, before Willian Pacho inadvertently directed the ball into his own net for an own-goal.
In a remarkable turn of fortune, Goncalo Ramos grabbed a crucial equaliser in the dying seconds to send the match into a deciding shootout. PSG goalkeeper Chevalier then emerged as the key figure, saving decisive kicks from O'Riley and Hamed Traore.
In the shootout, Ramos, the midfielder, the full-back, and Desire Doue all converted with composure for PSG to seal a convincing penalty victory.
The record winners Paris Saint-Germain, who faced last season's Ligue 1 second-placed team Marseille after achieving a domestic double, have now lifted this trophy for the 12th time in the last thirteen seasons.
