PSG has now claimed the season-opening trophy on 14 separate times.
The Parisian giants needed a stoppage-time equaliser followed by a perfect spot-kick decider to get past their arch-rivals in Kuwait and capture a fourth straight Trophee des Champions victory.
The European champions seemed to be sailing towards a straightforward triumph in the match featuring the Ligue 1 champions and the Coupe de France holders after the French winger found the net in the opening stages.
However, Marseille struck two times late to take a surprise advantage. Initially, the English forward scored from the penalty spot, before the defender unfortunately turned the ball into his own net for an own goal.
In a breathtaking turn of fortune, Goncalo Ramos grabbed a crucial equaliser in the final seconds to force the match into a deciding shootout. PSG goalkeeper Chevalier then stood as the hero, saving decisive attempts from O'Riley and Traore.
From the spot, Ramos, Vitinha, Nuno Mendes, and the young talent all scored with composure for Paris Saint-Germain to seal a 4-1 penalty victory.
Now 14-time winners Paris Saint-Germain, who faced last season's Ligue 1 second-placed team Olympique de Marseille after completing a league and cup double, have now lifted this competition for the twelfth time in the past 13 seasons.
