PSG has now claimed the prestigious cup on 14 separate times.
The Parisian giants needed a dramatic equaliser followed by a perfect penalty shootout to get past Marseille in the Gulf and secure a fourth straight French Super Cup victory.
The European champions seemed to be sailing towards a comfortable triumph in the showdown between the Ligue 1 winners and the French Cup winners after Ousmane Dembele opened the net in the opening stages.
Yet, the southern French side fired twice in the closing moments to take a surprise lead. Initially, the English forward converted from the penalty spot, before the defender inadvertently directed the ball into his own net for an own goal.
In a breathtaking turn of events, the Portuguese striker grabbed a crucial equaliser in the final moments to send the match into a penalty shootout. PSG goalkeeper Lucas Chevalier then emerged as the key figure, stopping decisive attempts from Matt O'Riley and Hamed Traore.
In the shootout, Goncalo Ramos, the midfielder, the full-back, and Desire Doue all converted with composure for Paris Saint-Germain to complete a convincing penalty win.
The record winners Paris Saint-Germain, who faced last season's Ligue 1 second-placed team Olympique de Marseille after completing a domestic double, have now won this trophy for the 12th time in the last 13 years.
