The Parisian club has now won the prestigious cup on fourteen different occasions.
Paris Saint-Germain required a stoppage-time leveler followed by a perfect spot-kick decider to overcome their arch-rivals in Kuwait and secure a record-extending fourth consecutive Trophee des Champions title.
The Champions League holders appeared to be coasting towards a straightforward win in the match featuring the Ligue 1 winners and the French Cup winners after Ousmane Dembele opened the net early on.
However, Marseille struck two times in the closing moments to take a shock lead. First, the English forward converted from the penalty spot, before Willian Pacho inadvertently directed the ball into his own net for an own-goal.
In a remarkable twist of fortune, Goncalo Ramos snatched a crucial equaliser in the final moments to send the match into a penalty shootout. The Parisian shot-stopper Lucas Chevalier then emerged as the hero, stopping crucial kicks from O'Riley and Traore.
In the shootout, Goncalo Ramos, Vitinha, the full-back, and Desire Doue all scored successfully for PSG to seal a 4-1 penalty win.
The record winners PSG, who met last season's Ligue 1 second-placed team Marseille after achieving a league and cup double, have now lifted this trophy for the 12th time in the past thirteen years.
