PSG has now won the season-opening cup on fourteen different times.
Paris Saint-Germain required a stoppage-time leveler followed by a successful spot-kick decider to overcome Marseille in Kuwait and capture a fourth straight Trophee des Champions title.
The Champions League holders appeared to be coasting towards a straightforward win in the match featuring the French league winners and the Coupe de France winners after the French winger found the scoring in the opening stages.
However, Marseille struck two times in the closing moments to take a surprise lead. First, the English forward converted from the penalty spot, before Willian Pacho unfortunately directed the ball into his own net for an own goal.
In a remarkable turn of events, Goncalo Ramos grabbed a crucial leveler in the dying seconds to force the match into a deciding shootout. PSG goalkeeper Chevalier then stood as the hero, stopping decisive attempts from O'Riley and Hamed Traore.
In the shootout, Goncalo Ramos, Vitinha, Nuno Mendes, and the young talent all converted successfully for PSG to complete a 4-1 shootout win.
The record champions Paris Saint-Germain, who met last season's Ligue 1 second-placed team Olympique de Marseille after achieving a league and cup double, have now won this competition for the twelfth time in the past thirteen seasons.
