PSG has now won the prestigious cup on 14 different times.
The Parisian giants needed a stoppage-time leveler followed by a successful penalty shootout to get past their arch-rivals in the Gulf and secure a record-extending fourth consecutive French Super Cup victory.
The European champions appeared to be coasting towards a straightforward win in the showdown between the Ligue 1 winners and the French Cup holders after Ousmane Dembele found the net in the opening stages.
However, Marseille fired twice in the closing moments to take a surprise lead. First, Mason Greenwood scored from the penalty spot, before the defender inadvertently turned the ball into his own net for an own goal.
In a breathtaking turn of events, the Portuguese striker grabbed a vital equaliser in the final moments to send the match into a penalty shootout. PSG goalkeeper Chevalier then emerged as the key figure, stopping crucial kicks from Matt O'Riley and Traore.
In the shootout, Ramos, Vitinha, Nuno Mendes, and the young talent all converted successfully for Paris Saint-Germain to complete a convincing shootout victory.
The record champions Paris Saint-Germain, who faced last season's Ligue 1 runners-up Marseille after completing a league and cup double, have now won this competition for the 12th time in the past 13 years.
