The Parisian club has now secured the prestigious trophy on fourteen separate occasions.
The Parisian giants needed a stoppage-time leveler followed by a perfect penalty shootout to overcome their arch-rivals in the Gulf and secure a fourth straight French Super Cup title.
The Champions League holders appeared to be sailing towards a comfortable win in the match featuring the Ligue 1 champions and the Coupe de France winners after the French winger found the net in the opening stages.
However, the southern French side struck twice in the closing moments to seize a surprise lead. First, the English forward converted from the penalty spot, before the defender inadvertently directed the ball into his own net for an own-goal.
In a breathtaking turn of fortune, the Portuguese striker grabbed a crucial leveler in the final seconds to send the contest into a deciding shootout. The Parisian shot-stopper Chevalier then stood as the key figure, saving decisive kicks from O'Riley and Hamed Traore.
From the spot, Goncalo Ramos, Vitinha, the full-back, and Desire Doue all converted with composure for PSG to complete a 4-1 penalty win.
The record champions Paris Saint-Germain, who faced last season's Ligue 1 second-placed team Olympique de Marseille after completing a domestic double, have now lifted this competition for the twelfth time in the last 13 years.
