The Parisian club has now won the season-opening cup on 14 different occasions.
Paris Saint-Germain needed a dramatic equaliser followed by a successful penalty shootout to get past Marseille in Kuwait and capture a record-extending fourth consecutive French Super Cup victory.
The Champions League holders seemed to be coasting towards a straightforward win in the match featuring the Ligue 1 winners and the French Cup holders after Ousmane Dembele opened the net in the opening stages.
However, the southern French side fired twice in the closing moments to take a shock lead. First, Mason Greenwood scored from the penalty spot, before Willian Pacho inadvertently turned the ball into his own net for an own goal.
In a breathtaking twist of fortune, Goncalo Ramos snatched a vital equaliser in the dying moments to send the match into a penalty shootout. The Parisian shot-stopper Chevalier then stood as the hero, saving decisive attempts from Matt O'Riley and Hamed Traore.
In the shootout, Ramos, Vitinha, the full-back, and Desire Doue all converted with composure for PSG to seal a convincing shootout victory.
The record champions Paris Saint-Germain, who faced last season's Ligue 1 second-placed team Marseille after completing a domestic double, have now won this trophy for the 12th time in the last 13 seasons.
