PSG has now secured the season-opening trophy on 14 separate times.
The Parisian giants needed a dramatic equaliser followed by a perfect penalty shootout to overcome Marseille in the Gulf and secure a record-extending fourth consecutive French Super Cup title.
The European champions appeared to be coasting towards a straightforward win in the showdown featuring the Ligue 1 winners and the Coupe de France winners after the French winger found the net in the opening stages.
However, Marseille struck twice late to take a surprise lead. First, Mason Greenwood converted from the spot-kick, before the defender unfortunately turned the ball into his own net for an own-goal.
In a breathtaking turn of events, the Portuguese striker grabbed a vital leveler in the final seconds to force the contest into a penalty shootout. The Parisian shot-stopper Lucas Chevalier then stood as the key figure, stopping decisive kicks from O'Riley and Traore.
In the shootout, Goncalo Ramos, Vitinha, the full-back, and Desire Doue all converted with composure for PSG to complete a convincing penalty victory.
The record winners PSG, who faced last season's Ligue 1 runners-up Marseille after completing a domestic double, have now lifted this trophy for the twelfth time in the last thirteen seasons.