PSG has now secured the season-opening cup on 14 separate times.
Paris Saint-Germain required a dramatic leveler followed by a perfect penalty shootout to overcome Marseille in the Gulf and secure a fourth straight French Super Cup victory.
The Champions League holders appeared to be coasting towards a straightforward triumph in the match between the Ligue 1 winners and the Coupe de France holders after the French winger found the net in the opening stages.
However, the southern French side struck two times late to seize a surprise lead. First, the English forward converted from the spot-kick, before Willian Pacho inadvertently directed the ball into his own net for an own goal.
In a breathtaking turn of fortune, the Portuguese striker grabbed a vital equaliser in the dying seconds to send the contest into a penalty shootout. PSG goalkeeper Lucas Chevalier then stood as the hero, saving decisive attempts from O'Riley and Traore.
From the spot, Ramos, Vitinha, the full-back, and the young talent all scored with composure for PSG to complete a 4-1 shootout win.
Now 14-time winners Paris Saint-Germain, who met last season's Ligue 1 runners-up Olympique de Marseille after completing a domestic double, have now lifted this competition for the 12th time in the past 13 seasons.