PSG has now secured the season-opening cup on 14 separate times.
The Parisian giants required a dramatic equaliser followed by a successful spot-kick decider to overcome Marseille in the Gulf and secure a record-extending fourth consecutive French Super Cup title.
The Champions League holders seemed to be coasting towards a comfortable win in the showdown featuring the Ligue 1 winners and the Coupe de France holders after the French winger found the scoring in the opening stages.
Yet, the southern French side struck twice in the closing moments to seize a shock lead. Initially, the English forward converted from the penalty spot, before Willian Pacho inadvertently directed the ball into his own net for an own goal.
In a breathtaking twist of fortune, the Portuguese striker grabbed a vital leveler in the final seconds to send the contest into a deciding shootout. The Parisian shot-stopper Lucas Chevalier then emerged as the key figure, saving decisive attempts from O'Riley and Traore.
From the spot, Goncalo Ramos, the midfielder, the full-back, and the young talent all scored with composure for PSG to complete a convincing shootout victory.
The record winners PSG, who met last season's Ligue 1 second-placed team Marseille after achieving a league and cup double, have now won this trophy for the 12th time in the last 13 years.