PSG has now secured the season-opening trophy on 14 different times.
The Parisian giants required a dramatic equaliser followed by a successful penalty shootout to get past their arch-rivals in Kuwait and capture a record-extending fourth consecutive French Super Cup title.
The European champions appeared to be coasting towards a comfortable win in the match featuring the Ligue 1 winners and the French Cup holders after the French winger found the scoring in the opening stages.
Yet, the southern French side fired two times late to take a shock advantage. Initially, Mason Greenwood scored from the penalty spot, before Willian Pacho inadvertently directed the ball into his own net for an own goal.
In a breathtaking turn of events, the Portuguese striker snatched a vital equaliser in the final moments to force the contest into a penalty shootout. PSG goalkeeper Chevalier then emerged as the key figure, stopping crucial kicks from O'Riley and Traore.
From the spot, Goncalo Ramos, the midfielder, the full-back, and Desire Doue all scored with composure for Paris Saint-Germain to complete a 4-1 shootout victory.
The record champions Paris Saint-Germain, who faced last season's Ligue 1 runners-up Marseille after achieving a domestic double, have now lifted this competition for the twelfth time in the past thirteen seasons.
