The Parisian club has now secured the season-opening cup on 14 different times.
The Parisian giants needed a dramatic leveler followed by a perfect spot-kick decider to overcome their arch-rivals in Kuwait and secure a record-extending fourth consecutive French Super Cup victory.
The European champions seemed to be sailing towards a straightforward win in the match between the French league champions and the Coupe de France holders after the French winger found the net in the opening stages.
However, the southern French side struck twice late to take a shock lead. Initially, Mason Greenwood scored from the penalty spot, before the defender unfortunately directed the ball into his own net for an own goal.
In a remarkable turn of fortune, Goncalo Ramos grabbed a crucial equaliser in the final seconds to send the match into a penalty shootout. The Parisian shot-stopper Lucas Chevalier then stood as the hero, saving crucial kicks from Matt O'Riley and Hamed Traore.
From the spot, Ramos, the midfielder, Nuno Mendes, and the young talent all scored successfully for Paris Saint-Germain to seal a 4-1 shootout victory.
The record champions Paris Saint-Germain, 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 twelfth time in the past 13 years.
