The Parisian club has now won the season-opening trophy on 14 different times.
Paris Saint-Germain needed a dramatic equaliser followed by a perfect spot-kick decider to get past Marseille in Kuwait and secure a fourth straight French Super Cup title.
The Champions League holders appeared to be coasting towards a comfortable win in the showdown featuring the French league winners and the Coupe de France holders after the French winger opened the scoring early on.
However, the southern French side struck twice late to seize a surprise lead. 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 breathtaking turn of fortune, Goncalo Ramos grabbed a vital equaliser in the dying seconds to force the match into a penalty shootout. The Parisian shot-stopper Lucas Chevalier then stood as the key figure, saving crucial kicks from O'Riley and Traore.
From the spot, Ramos, Vitinha, the full-back, and the young talent all scored successfully for PSG to complete a 4-1 shootout victory.
Now 14-time winners Paris Saint-Germain, who faced last season's Ligue 1 second-placed team Olympique de Marseille after achieving a domestic double, have now lifted this competition for the twelfth time in the past 13 years.
