The Parisian club has now claimed the prestigious cup on 14 separate times.
Paris Saint-Germain needed 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 seemed to be coasting towards a straightforward triumph in the match featuring the French league champions and the French Cup winners after the French winger opened the scoring early on.
However, the southern French side fired twice in the closing moments to seize a shock lead. First, the English forward scored 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, the Portuguese striker snatched a vital equaliser in the final seconds to force the match into a penalty shootout. PSG goalkeeper Chevalier then stood as the hero, stopping crucial kicks from O'Riley and Hamed Traore.
From the spot, Ramos, the midfielder, Nuno Mendes, and Desire Doue all scored successfully for Paris Saint-Germain to complete a 4-1 shootout victory.
The record champions 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 past 13 seasons.
