PSG has now won the season-opening trophy on 14 different occasions.
The Parisian giants required a stoppage-time equaliser followed by a successful spot-kick decider to get past Marseille in Kuwait and secure a record-extending fourth consecutive French Super Cup victory.
The European champions appeared to be sailing towards a straightforward triumph in the showdown between the Ligue 1 winners and the French Cup holders after the French winger found the scoring early on.
However, the southern French side struck twice in the closing moments to take a surprise advantage. First, Mason Greenwood scored from the spot-kick, before the defender unfortunately directed the ball into his own net for an own goal.
In a remarkable twist of events, Goncalo Ramos snatched a crucial leveler in the dying moments to force the match into a penalty shootout. PSG goalkeeper Chevalier then emerged as the key figure, saving decisive attempts from O'Riley and Hamed Traore.
In the shootout, Ramos, Vitinha, the full-back, and the young talent all converted successfully for Paris Saint-Germain to complete a 4-1 shootout win.
Now 14-time champions PSG, who faced last season's Ligue 1 runners-up Marseille after achieving a domestic double, have now won this trophy for the twelfth time in the past thirteen years.
