PSG has now won the season-opening cup on 14 separate times.
The Parisian giants needed a stoppage-time equaliser followed by a successful penalty shootout to get past their arch-rivals in the Gulf and secure a record-extending fourth consecutive Trophee des Champions title.
The European champions appeared to be sailing towards a comfortable triumph in the showdown between the French league champions and the Coupe de France holders after Ousmane Dembele found the net in the opening stages.
However, Marseille struck twice in the closing moments to seize a surprise advantage. Initially, Mason Greenwood converted from the penalty spot, before the defender unfortunately turned the ball into his own net for an own goal.
In a remarkable twist of events, Goncalo Ramos grabbed a vital leveler in the final moments to force the contest into a deciding shootout. The Parisian shot-stopper Chevalier then emerged as the hero, stopping crucial attempts from O'Riley and Hamed Traore.
In the shootout, Ramos, the midfielder, the full-back, and Desire Doue all scored with composure for PSG to seal a 4-1 penalty win.
Now 14-time champions PSG, 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 last 13 years.
