PSG has now claimed the prestigious trophy on 14 separate times.
The Parisian giants required a stoppage-time equaliser followed by a perfect spot-kick decider to overcome Marseille in the Gulf and secure a fourth straight French Super Cup title.
The Champions League holders seemed to be coasting towards a comfortable triumph in the match featuring the Ligue 1 winners and the French Cup winners after the French winger found the scoring in the opening stages.
However, the southern French side fired twice late to seize a shock advantage. Initially, the English forward converted from the spot-kick, before the defender unfortunately directed the ball into his own net for an own goal.
In a remarkable twist of events, Goncalo Ramos snatched a crucial equaliser in the dying seconds to send the match into a penalty shootout. The Parisian shot-stopper Chevalier then stood as the hero, saving crucial attempts from O'Riley and Hamed Traore.
In the shootout, Ramos, Vitinha, the full-back, and the young talent all converted with composure for PSG to complete a convincing shootout victory.
Now 14-time winners PSG, who faced last season's Ligue 1 second-placed team Marseille after completing a league and cup double, have now won this competition for the twelfth time in the last 13 years.
