The Parisian club has now claimed the season-opening trophy on 14 separate times.
Paris Saint-Germain required a dramatic equaliser 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 straightforward win in the match featuring the Ligue 1 champions and the French Cup winners after the French winger found the scoring in the opening stages.
Yet, the southern French side struck two times late to take a surprise advantage. Initially, the English forward scored 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, the Portuguese striker grabbed a crucial leveler in the final moments to send the match into a deciding shootout. PSG goalkeeper Lucas Chevalier then stood as the hero, saving decisive attempts from O'Riley and Hamed Traore.
In the shootout, Ramos, Vitinha, the full-back, and Desire Doue all converted with composure for PSG to complete a convincing shootout win.
The record champions PSG, who faced last season's Ligue 1 second-placed team Marseille after completing a domestic double, have now won this trophy for the 12th time in the last thirteen years.