PSG has now secured the season-opening trophy 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 capture a fourth straight French Super Cup victory.
The Champions League holders appeared to be coasting towards a straightforward win in the match between the French league winners and the Coupe de France holders after Ousmane Dembele opened the net in the opening stages.
However, Marseille struck two times in the closing moments to seize a shock lead. First, Mason Greenwood converted from the spot-kick, before the defender unfortunately turned the ball into his own net for an own-goal.
In a remarkable turn of events, Goncalo Ramos snatched a vital equaliser in the final moments to send the contest into a penalty shootout. The Parisian shot-stopper Chevalier then emerged as the key figure, saving decisive attempts from Matt O'Riley and Hamed Traore.
From the spot, Goncalo Ramos, Vitinha, Nuno Mendes, and the young talent all converted with composure for PSG to seal a 4-1 shootout win.
The record winners PSG, who met last season's Ligue 1 runners-up Olympique de Marseille after achieving a domestic double, have now lifted this competition for the 12th time in the last 13 years.
