The Parisian club has now won the prestigious trophy on 14 separate times.
The Parisian giants required a dramatic equaliser followed by a perfect penalty shootout to overcome Marseille in Kuwait and capture a record-extending fourth consecutive French Super Cup victory.
The Champions League holders seemed to be sailing towards a straightforward triumph in the showdown featuring the Ligue 1 winners and the French Cup winners after the French winger opened the net early on.
However, Marseille struck twice late to take a surprise advantage. Initially, Mason Greenwood converted from the spot-kick, before Willian Pacho unfortunately turned the ball into his own net for an own goal.
In a remarkable turn of fortune, the Portuguese striker grabbed a vital equaliser in the final seconds to send the contest into a penalty shootout. The Parisian shot-stopper Lucas Chevalier then emerged as the key figure, saving decisive attempts from O'Riley and Traore.
In the shootout, Ramos, Vitinha, Nuno Mendes, and Desire Doue all scored successfully for Paris Saint-Germain to complete a 4-1 shootout victory.
Now 14-time winners Paris Saint-Germain, who faced last season's Ligue 1 runners-up Marseille after achieving a league and cup double, have now lifted this trophy for the twelfth time in the past 13 years.