The Parisian club has now won the prestigious cup on fourteen different times.
Paris Saint-Germain needed a stoppage-time equaliser followed by a successful spot-kick decider to overcome Marseille in Kuwait and secure a record-extending fourth consecutive Trophee des Champions victory.
The European champions seemed to be sailing towards a comfortable triumph in the match between the Ligue 1 winners and the Coupe de France winners after the French winger opened the net in the opening stages.
However, the southern French side struck two times late to take a shock advantage. First, the English forward scored from the penalty spot, before Willian Pacho unfortunately directed the ball into his own net for an own goal.
In a remarkable twist of events, the Portuguese striker grabbed a vital leveler in the final moments to send the match into a penalty shootout. PSG goalkeeper Chevalier then emerged as the hero, saving decisive attempts from O'Riley and Traore.
From the spot, Goncalo Ramos, Vitinha, Nuno Mendes, and the young talent all scored successfully for PSG to seal a 4-1 shootout win.
Now 14-time champions Paris Saint-Germain, who faced last season's Ligue 1 runners-up Olympique de Marseille after achieving a domestic double, have now lifted this competition for the twelfth time in the last thirteen years.