PSG has now won the prestigious trophy on fourteen separate occasions.
The Parisian giants needed a dramatic equaliser followed by a successful penalty shootout 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 coasting towards a straightforward triumph in the match between the French league champions and the French Cup winners after Ousmane Dembele found the net in the opening stages.
However, the southern French side fired twice in the closing moments to seize a surprise lead. First, the English forward scored from the spot-kick, before Willian Pacho inadvertently directed the ball into his own net for an own goal.
In a breathtaking turn of fortune, Goncalo Ramos snatched a vital equaliser in the final seconds to send the match into a deciding shootout. PSG goalkeeper Lucas Chevalier then emerged as the hero, stopping decisive attempts from O'Riley and Hamed Traore.
In the shootout, Goncalo Ramos, Vitinha, the full-back, and the young talent all converted successfully for PSG to complete a 4-1 shootout victory.
The record winners PSG, who met last season's Ligue 1 runners-up Olympique de Marseille after completing a domestic double, have now lifted this trophy for the 12th time in the last 13 years.