The Parisian club has now won the season-opening cup on 14 separate times.
The Parisian giants required a dramatic leveler followed by a successful spot-kick decider to get past their arch-rivals in the Gulf and secure a record-extending fourth consecutive French Super Cup title.
The European champions seemed to be coasting towards a comfortable win in the showdown between the Ligue 1 winners and the French Cup holders after Ousmane Dembele found the net in the opening stages.
However, the southern French side struck two times late to seize a surprise lead. Initially, Mason Greenwood converted from the penalty spot, before Willian Pacho inadvertently directed the ball into his own net for an own-goal.
In a remarkable turn of fortune, Goncalo Ramos snatched a vital equaliser in the final moments to send the match into a penalty shootout. PSG goalkeeper Lucas Chevalier then emerged as the hero, stopping crucial kicks from O'Riley and Hamed Traore.
In the shootout, Goncalo Ramos, Vitinha, the full-back, and Desire Doue all scored successfully for PSG to seal a convincing shootout victory.
Now 14-time champions PSG, who met last season's Ligue 1 runners-up Marseille after completing a domestic double, have now won this competition for the twelfth time in the last 13 years.