The Parisian club has now claimed the season-opening cup on fourteen 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 fourth straight French Super Cup title.
The Champions League holders seemed to be sailing towards a comfortable triumph in the match 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 twice late to take a shock advantage. Initially, the English forward converted from the spot-kick, before the defender unfortunately directed the ball into his own net for an own goal.
In a remarkable turn of fortune, Goncalo Ramos snatched a crucial leveler in the dying moments to force the contest into a deciding shootout. PSG goalkeeper Lucas Chevalier then emerged as the hero, saving crucial attempts from Matt O'Riley and Hamed Traore.
From the spot, Goncalo Ramos, Vitinha, Nuno Mendes, and Desire Doue all converted successfully for Paris Saint-Germain to complete a 4-1 shootout victory.
Now 14-time champions PSG, who faced last season's Ligue 1 runners-up Olympique de Marseille after completing a league and cup double, have now won this trophy for the twelfth time in the last 13 years.