PSG has now won the prestigious cup on 14 separate times.
Paris Saint-Germain required a stoppage-time equaliser followed by a successful 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 showdown between the Ligue 1 champions and the French Cup winners after Ousmane Dembele found the net early on.
However, the southern French side struck two times in the closing moments to seize a shock advantage. First, Mason Greenwood converted from the spot-kick, before Willian Pacho unfortunately turned the ball into his own net for an own goal.
In a remarkable twist of fortune, Goncalo Ramos grabbed a vital leveler in the dying moments to force the contest into a deciding shootout. PSG goalkeeper Chevalier then stood as the key figure, saving decisive attempts from O'Riley and Traore.
From the spot, Ramos, the midfielder, Nuno Mendes, and the young talent all scored with composure for Paris Saint-Germain to seal a convincing penalty victory.
The record champions PSG, who met last season's Ligue 1 runners-up Marseille after completing a league and cup double, have now won this competition for the 12th time in the past 13 years.
