PSG has now won the season-opening cup on 14 different occasions.
The Parisian giants needed a dramatic leveler followed by a perfect spot-kick decider to get past Marseille in the Gulf and secure a fourth straight French Super Cup victory.
The Champions League holders appeared to be sailing towards a comfortable triumph in the match between the Ligue 1 champions and the Coupe de France winners after the French winger found the net in the opening stages.
However, Marseille struck two times late to take a shock lead. Initially, Mason Greenwood scored from the penalty spot, before Willian Pacho unfortunately directed the ball into his own net for an own-goal.
In a remarkable twist of fortune, the Portuguese striker grabbed a crucial leveler in the dying seconds to force the contest into a deciding shootout. PSG goalkeeper Lucas Chevalier then emerged as the key figure, saving crucial kicks from O'Riley and Hamed Traore.
From the spot, Ramos, Vitinha, the full-back, and the young talent all scored successfully for Paris Saint-Germain to complete a convincing shootout victory.
The record winners PSG, who met last season's Ligue 1 second-placed team Olympique de Marseille after achieving a league and cup double, have now won this competition for the 12th time in the last 13 seasons.
