The Parisian club has now secured the prestigious trophy on fourteen different occasions.
The Parisian giants needed a dramatic leveler followed by a perfect penalty shootout to get past their arch-rivals in the Gulf and secure a record-extending fourth consecutive French Super Cup title.
The Champions League holders appeared to be coasting towards a straightforward win in the match featuring the Ligue 1 champions and the French Cup holders after Ousmane Dembele opened the scoring in the opening stages.
However, the southern French side struck two times late to take a surprise advantage. Initially, Mason Greenwood converted from the penalty spot, before the defender unfortunately turned the ball into his own net for an own-goal.
In a breathtaking twist of fortune, Goncalo Ramos snatched a vital equaliser in the final seconds to force the contest into a penalty shootout. The Parisian shot-stopper Lucas Chevalier then emerged as the key figure, saving decisive attempts from O'Riley and Traore.
From the spot, Ramos, Vitinha, Nuno Mendes, and the young talent all converted with composure for Paris Saint-Germain to complete a 4-1 penalty win.
Now 14-time champions PSG, who faced last season's Ligue 1 second-placed team Marseille after completing a league and cup double, have now won this trophy for the twelfth time in the past 13 years.