PSG has now won the prestigious trophy on 14 separate occasions.
The Parisian giants required a dramatic equaliser followed by a perfect spot-kick decider to overcome Marseille in Kuwait and capture a fourth straight French Super Cup title.
The European champions appeared to be coasting towards a straightforward triumph in the showdown between the Ligue 1 winners and the French Cup winners after Ousmane Dembele found the net in the opening stages.
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 turn of events, the Portuguese striker snatched a vital equaliser in the dying seconds to force the match into a deciding shootout. The Parisian shot-stopper Chevalier then emerged as the key figure, saving crucial kicks from O'Riley and Traore.
In the shootout, Goncalo Ramos, the midfielder, Nuno Mendes, and Desire Doue all converted with composure for PSG to complete a 4-1 shootout victory.
Now 14-time champions Paris Saint-Germain, who faced last season's Ligue 1 second-placed team Olympique de Marseille after achieving a domestic double, have now won this trophy for the 12th time in the last thirteen years.
