The Parisian club has now won the season-opening cup on 14 different occasions.
The Parisian giants required a dramatic equaliser followed by a perfect penalty shootout to get past Marseille in Kuwait and capture a fourth straight French Super Cup title.
The Champions League holders appeared to be sailing towards a comfortable triumph in the match featuring the Ligue 1 winners and the Coupe de France holders after Ousmane Dembele found the scoring in the opening stages.
However, the southern French side struck twice in the closing moments to take a shock advantage. Initially, the English forward scored from the penalty spot, before Willian Pacho inadvertently turned the ball into his own net for an own-goal.
In a breathtaking turn of fortune, the Portuguese striker grabbed a vital leveler in the dying moments to send the contest into a penalty shootout. PSG goalkeeper Chevalier then stood as the hero, stopping crucial attempts from O'Riley and Traore.
From the spot, Goncalo Ramos, Vitinha, Nuno Mendes, and the young talent all converted with composure for Paris Saint-Germain to seal a 4-1 penalty victory.
The record 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 12th time in the last 13 years.
