PSG has now secured the prestigious trophy on fourteen different occasions.
The Parisian giants needed a dramatic equaliser followed by a successful spot-kick decider to overcome their arch-rivals in the Gulf and capture a record-extending fourth consecutive French Super Cup title.
The European champions seemed to be sailing towards a straightforward triumph in the showdown featuring the French league champions and the Coupe de France winners after the French winger found the scoring early on.
However, the southern French side fired two times late to take a surprise advantage. Initially, the English forward converted from the penalty spot, before the defender unfortunately directed the ball into his own net for an own-goal.
In a breathtaking turn of fortune, the Portuguese striker snatched a vital leveler in the dying seconds to send the match into a deciding shootout. PSG goalkeeper Lucas Chevalier then stood as the key figure, stopping decisive kicks from Matt O'Riley and Hamed Traore.
In the shootout, Goncalo Ramos, the midfielder, the full-back, and Desire Doue all converted with composure for PSG to seal a convincing shootout victory.
The record champions PSG, who faced last season's Ligue 1 runners-up Marseille after achieving a league and cup double, have now lifted this competition for the twelfth time in the last 13 years.