PSG has now secured the prestigious cup on 14 separate times.
The Parisian giants needed a stoppage-time equaliser followed by a perfect penalty shootout to get past their arch-rivals in Kuwait and capture a fourth straight French Super Cup title.
The European champions appeared to be coasting towards a straightforward win in the match featuring the Ligue 1 winners and the Coupe de France holders after the French winger opened the scoring in the opening stages.
Yet, the southern French side struck twice in the closing moments to seize a shock advantage. Initially, Mason Greenwood converted from the penalty spot, before Willian Pacho unfortunately directed the ball into his own net for an own-goal.
In a remarkable turn of fortune, Goncalo Ramos snatched a vital leveler in the final moments to force the match into a penalty shootout. PSG goalkeeper Chevalier then emerged as the key figure, saving crucial kicks from O'Riley and Hamed Traore.
From the spot, Goncalo Ramos, the midfielder, the full-back, and Desire Doue all scored successfully for PSG to seal a 4-1 penalty victory.
Now 14-time winners PSG, who met last season's Ligue 1 second-placed team Olympique de Marseille after achieving a domestic double, have now won this trophy for the 12th time in the last 13 years.
