PSG has now claimed the prestigious cup on 14 separate occasions.
The Parisian giants needed a dramatic equaliser followed by a perfect spot-kick decider to overcome Marseille in the Gulf and secure a fourth straight Trophee des Champions title.
The European champions appeared to be sailing towards a comfortable triumph in the match featuring the French league winners and the Coupe de France winners after the French winger found the net in the opening stages.
However, Marseille struck twice late to take a surprise advantage. Initially, the English forward converted from the penalty spot, before the defender inadvertently directed the ball into his own net for an own-goal.
In a breathtaking twist of fortune, Goncalo Ramos grabbed a vital leveler in the dying seconds to force the contest into a penalty shootout. PSG goalkeeper Chevalier then stood as the hero, saving decisive kicks from O'Riley and Traore.
From the spot, Goncalo Ramos, Vitinha, Nuno Mendes, and the young talent all converted with composure for PSG to seal a 4-1 penalty victory.
The record winners Paris Saint-Germain, who faced last season's Ligue 1 runners-up Olympique de Marseille after completing a league and cup double, have now won this competition for the twelfth time in the past 13 years.
