The Parisian club has now won the prestigious trophy on 14 different occasions.
The Parisian giants needed a stoppage-time equaliser followed by a perfect spot-kick decider to overcome their arch-rivals in Kuwait and capture a fourth straight French Super Cup victory.
The Champions League holders appeared to be coasting towards a comfortable win in the match featuring the French league winners and the French Cup winners after Ousmane Dembele found the scoring early on.
However, the southern French side struck twice in the closing moments to take a surprise advantage. Initially, Mason Greenwood converted from the penalty spot, before the defender unfortunately directed the ball into his own net for an own-goal.
In a remarkable turn of events, the Portuguese striker grabbed a crucial equaliser in the final moments to force the contest into a penalty shootout. PSG goalkeeper Chevalier then emerged as the key figure, saving decisive kicks from Matt O'Riley and Hamed Traore.
From the spot, Ramos, Vitinha, the full-back, and the young talent all scored successfully for PSG to complete a convincing shootout win.
The record champions Paris Saint-Germain, who faced last season's Ligue 1 runners-up Marseille after achieving a league and cup double, have now won this competition for the twelfth time in the past 13 seasons.
