PSG has now secured the season-opening cup on 14 separate occasions.
The Parisian giants required a dramatic equaliser followed by a perfect penalty shootout to overcome their arch-rivals in the Gulf and capture a record-extending fourth consecutive French Super Cup title.
The Champions League holders appeared to be sailing towards a straightforward triumph in the match featuring the Ligue 1 champions and the French Cup holders after the French winger found the net early on.
Yet, the southern French side struck two times late to seize a shock advantage. Initially, Mason Greenwood scored from the spot-kick, before the defender unfortunately turned the ball into his own net for an own-goal.
In a remarkable turn of fortune, the Portuguese striker grabbed a crucial leveler in the final moments to send the match into a deciding shootout. The Parisian shot-stopper Lucas Chevalier then emerged as the hero, stopping crucial kicks from Matt O'Riley and Hamed Traore.
In the shootout, Goncalo Ramos, the midfielder, the full-back, and Desire Doue all scored successfully for PSG to complete a 4-1 shootout win.
Now 14-time champions Paris Saint-Germain, who faced last season's Ligue 1 second-placed team Marseille after completing a league and cup double, have now lifted this trophy for the twelfth time in the last thirteen seasons.