The Parisian club has now won the prestigious cup on 14 separate occasions.
The Parisian giants required a stoppage-time leveler followed by a perfect penalty shootout to get past Marseille in Kuwait and secure a record-extending fourth consecutive French Super Cup title.
The European champions appeared to be coasting towards a straightforward triumph in the showdown featuring the Ligue 1 winners and the Coupe de France winners after the French winger found the net early on.
Yet, the southern French side fired two times in the closing moments to take a shock advantage. First, Mason Greenwood scored from the penalty spot, before Willian Pacho inadvertently directed the ball into his own net for an own-goal.
In a remarkable turn of events, Goncalo Ramos snatched a vital equaliser in the dying seconds to send the contest into a penalty shootout. The Parisian shot-stopper Chevalier then emerged as the key figure, stopping crucial kicks from O'Riley and Hamed Traore.
From the spot, Ramos, Vitinha, the full-back, and Desire Doue all converted successfully for Paris Saint-Germain to seal a convincing shootout victory.
The record champions Paris Saint-Germain, who faced last season's Ligue 1 second-placed team Marseille after achieving a league and cup double, have now lifted this trophy for the 12th time in the last 13 seasons.
