The Parisian club has now claimed the prestigious cup on 14 separate times.
Paris Saint-Germain required a stoppage-time leveler followed by a successful penalty shootout to get past their arch-rivals in the Gulf and capture a record-extending fourth consecutive Trophee des Champions title.
The European champions seemed to be sailing towards a comfortable win in the match featuring the Ligue 1 winners and the French Cup holders after Ousmane Dembele found the scoring in the opening stages.
Yet, Marseille fired twice in the closing moments to seize a shock lead. Initially, Mason Greenwood scored from the penalty spot, before Willian Pacho inadvertently directed the ball into his own net for an own goal.
In a breathtaking twist of events, the Portuguese striker grabbed a vital leveler in the final seconds to send the match into a deciding shootout. PSG goalkeeper Lucas Chevalier then emerged as the hero, saving decisive kicks from O'Riley and Hamed Traore.
In the shootout, Goncalo Ramos, the midfielder, the full-back, and the young talent all scored with composure for PSG to seal a convincing shootout victory.
The record winners PSG, who faced last season's Ligue 1 runners-up Marseille after completing a domestic double, have now won this trophy for the 12th time in the last thirteen seasons.