PSG has now claimed the season-opening trophy on 14 separate times.
Paris Saint-Germain needed a dramatic leveler followed by a successful spot-kick decider to get past their arch-rivals in the Gulf and capture a record-extending fourth consecutive French Super Cup title.
The European champions appeared to be sailing towards a straightforward win in the showdown featuring the French league winners and the Coupe de France holders after Ousmane Dembele found the net early on.
However, the southern French side struck two times in the closing moments to seize a shock lead. Initially, the English forward scored from the penalty spot, before Willian Pacho unfortunately directed the ball into his own net for an own-goal.
In a remarkable turn of fortune, the Portuguese striker grabbed a vital leveler in the final seconds to force the match into a deciding shootout. PSG goalkeeper Lucas Chevalier then emerged as the hero, stopping decisive attempts from O'Riley and Hamed Traore.
From the spot, Ramos, the midfielder, the full-back, and the young talent all scored with composure for Paris Saint-Germain to complete a convincing penalty win.
Now 14-time winners PSG, who met last season's Ligue 1 second-placed team Marseille after achieving a domestic double, have now won this trophy for the twelfth time in the past 13 seasons.
