PSG has now secured the season-opening trophy on 14 separate times.
The Parisian giants needed a stoppage-time leveler followed by a perfect spot-kick decider to get past Marseille in the Gulf and capture a record-extending fourth consecutive Trophee des Champions title.
The European champions appeared to be sailing towards a comfortable win in the match featuring the Ligue 1 winners and the Coupe de France holders after Ousmane Dembele opened the net in the opening stages.
However, the southern French side fired twice in the closing moments to take a shock advantage. First, Mason Greenwood scored from the spot-kick, before the defender inadvertently turned the ball into his own net for an own goal.
In a breathtaking turn of events, Goncalo Ramos snatched a vital leveler in the dying moments to send the match into a deciding shootout. The Parisian shot-stopper Chevalier then stood as the key figure, stopping crucial attempts from O'Riley and Hamed Traore.
From the spot, Ramos, the midfielder, the full-back, and Desire Doue all scored successfully for PSG to seal a 4-1 penalty win.
The record winners Paris Saint-Germain, who met last season's Ligue 1 second-placed team Marseille after completing a domestic double, have now lifted this trophy for the twelfth time in the past thirteen years.
