The Parisian club has now won the season-opening trophy on fourteen different occasions.
Paris Saint-Germain required a dramatic leveler followed by a perfect spot-kick decider to get past Marseille in Kuwait and capture a fourth straight French Super Cup victory.
The European champions seemed to be sailing towards a comfortable triumph in the showdown featuring the Ligue 1 winners and the French Cup winners after Ousmane Dembele opened the scoring early on.
However, the southern French side fired twice late to take a surprise advantage. Initially, Mason Greenwood converted from the penalty spot, before Willian Pacho unfortunately turned the ball into his own net for an own goal.
In a remarkable turn of events, the Portuguese striker snatched a vital equaliser in the final moments to send the match into a deciding shootout. PSG goalkeeper Lucas Chevalier then stood as the hero, saving crucial attempts from O'Riley and Hamed Traore.
From the spot, Goncalo Ramos, Vitinha, Nuno Mendes, and the young talent all converted successfully for PSG to seal a convincing shootout victory.
Now 14-time champions PSG, who met last season's Ligue 1 second-placed team Marseille after achieving a league and cup double, have now won this competition for the 12th time in the past 13 years.
