PSG has now won the prestigious cup on fourteen separate times.
Paris Saint-Germain required a stoppage-time leveler followed by a successful spot-kick decider to get past Marseille in Kuwait and secure a fourth straight French Super Cup title.
The European champions seemed to be coasting towards a comfortable win in the match featuring the French league champions and the French Cup holders after the French winger found the net in the opening stages.
However, the southern French side fired two times in the closing moments to take a shock advantage. Initially, Mason Greenwood converted from the spot-kick, before the defender inadvertently turned the ball into his own net for an own goal.
In a remarkable twist of fortune, Goncalo Ramos snatched a vital leveler in the dying moments to send the contest into a penalty shootout. PSG goalkeeper Chevalier then stood as the key figure, stopping crucial attempts from O'Riley and Traore.
In the shootout, Ramos, the midfielder, Nuno Mendes, and Desire Doue all converted with composure for PSG to complete a convincing penalty victory.
Now 14-time winners PSG, who faced last season's Ligue 1 second-placed team Marseille after achieving a league and cup double, have now won this trophy for the twelfth time in the past 13 seasons.
