The Parisian club has now won the season-opening trophy on 14 separate times.
Paris Saint-Germain required a dramatic equaliser followed by a perfect spot-kick decider to get past their arch-rivals in the Gulf and capture a fourth straight French Super Cup victory.
The European champions appeared to be sailing towards a straightforward triumph in the match featuring the French league champions and the French Cup holders after Ousmane Dembele opened the scoring early on.
However, Marseille struck twice in the closing moments to take a surprise advantage. First, the English forward converted from the spot-kick, before Willian Pacho unfortunately turned the ball into his own net for an own-goal.
In a remarkable turn of fortune, the Portuguese striker snatched a crucial equaliser in the final seconds to force the match into a deciding shootout. PSG goalkeeper Chevalier then emerged as the key figure, saving crucial kicks from O'Riley and Hamed Traore.
In the shootout, Ramos, the midfielder, the full-back, and the young talent all scored with composure for PSG to complete a 4-1 shootout victory.
The record champions PSG, who faced last season's Ligue 1 second-placed team Marseille after completing a league and cup double, have now won this competition for the 12th time in the last thirteen years.
