PSG has now won the prestigious trophy on 14 separate times.
The Parisian giants required a dramatic leveler followed by a perfect spot-kick decider to get past 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 showdown featuring the French league winners and the French Cup holders after the French winger opened the scoring early on.
However, the southern French side fired twice in the closing moments to seize a surprise lead. First, Mason Greenwood scored from the penalty spot, before the defender unfortunately turned the ball into his own net for an own goal.
In a remarkable turn of events, the Portuguese striker snatched a crucial leveler in the final moments to send the contest into a deciding shootout. The Parisian shot-stopper Lucas Chevalier then stood as the key figure, stopping crucial kicks from Matt O'Riley and Hamed Traore.
In the shootout, Goncalo Ramos, Vitinha, the full-back, and Desire Doue all scored successfully for Paris Saint-Germain to complete a 4-1 shootout victory.
The record champions PSG, who faced last season's Ligue 1 second-placed team Olympique de Marseille after completing a league and cup double, have now won this competition for the 12th time in the past thirteen years.
