PSG has now won the season-opening trophy on 14 different occasions.
The Parisian giants required a dramatic leveler followed by a perfect spot-kick decider to get past their arch-rivals in Kuwait and secure a record-extending fourth consecutive Trophee des Champions victory.
The European champions appeared to be sailing towards a comfortable win in the match featuring the Ligue 1 winners and the French Cup holders after the French winger opened the scoring in the opening stages.
Yet, Marseille struck two times in the closing moments to seize a surprise advantage. First, the English forward scored from the spot-kick, before the defender inadvertently directed the ball into his own net for an own-goal.
In a breathtaking turn of fortune, the Portuguese striker snatched a vital equaliser in the dying seconds to force the contest into a deciding shootout. The Parisian shot-stopper Chevalier then stood as the key figure, stopping decisive kicks from Matt O'Riley and Traore.
From the spot, Ramos, the midfielder, the full-back, and the young talent all scored successfully for PSG to complete a 4-1 penalty victory.
The record champions Paris Saint-Germain, who faced last season's Ligue 1 runners-up Marseille after achieving a domestic double, have now won this competition for the 12th time in the last 13 years.
