PSG has now claimed the prestigious trophy on 14 different times.
Paris Saint-Germain required a stoppage-time leveler followed by a perfect penalty shootout to get past their arch-rivals in the Gulf and capture a fourth straight French Super Cup title.
The European champions appeared to be coasting towards a straightforward win in the match between the French league winners and the Coupe de France winners after Ousmane Dembele found the scoring in the opening stages.
However, the southern French side fired two times in the closing moments to take a shock advantage. Initially, Mason Greenwood scored from the spot-kick, before Willian Pacho unfortunately turned the ball into his own net for an own-goal.
In a remarkable turn of fortune, Goncalo Ramos grabbed a vital equaliser in the final seconds to send the match into a deciding shootout. PSG goalkeeper Lucas Chevalier then stood as the key figure, saving decisive attempts from Matt O'Riley and Hamed Traore.
In the shootout, Ramos, the midfielder, Nuno Mendes, and the young talent all scored with composure for Paris Saint-Germain to complete a convincing shootout victory.
The record champions PSG, who met last season's Ligue 1 second-placed team Olympique de Marseille after achieving a league and cup double, have now won this competition for the 12th time in the last thirteen seasons.
