PSG has now secured the season-opening cup on 14 different occasions.
The Parisian giants needed a stoppage-time leveler followed by a successful spot-kick decider to get past their arch-rivals in Kuwait and secure a fourth straight French Super Cup title.
The Champions League holders seemed to be coasting towards a straightforward win in the match featuring the French league winners and the Coupe de France holders after the French winger opened the net early on.
However, Marseille struck twice in the closing moments to seize a surprise lead. Initially, the English forward scored from the penalty spot, before Willian Pacho inadvertently turned the ball into his own net for an own-goal.
In a remarkable turn of fortune, Goncalo Ramos snatched a vital equaliser in the dying seconds to send the contest into a penalty shootout. PSG goalkeeper Chevalier then emerged as the key figure, saving crucial kicks from O'Riley and Traore.
In the shootout, Ramos, the midfielder, the full-back, and Desire Doue all converted with composure for Paris Saint-Germain to complete a 4-1 shootout victory.
The record winners Paris Saint-Germain, who faced last season's Ligue 1 runners-up Olympique de Marseille after achieving a domestic double, have now won this competition for the 12th time in the past 13 years.
