Les Parisiens were held to a 1-1 draw by Montpellier in the 2013-14 curtain raiser last Friday but will be determined for three points against Fabrizio Ravanelli's side
The champions' defence of their title - which they regained last term after a 19-year drought - did not get off to a flying start as they were held to a 1-1 at Montpellier last Friday.
But PSG boss Laurent Blanc will hope that home advantage will give them the edge over Fabrizio Ravanelli's Ajaccio, who were beaten by Saint-Etienne in their opening game of the season.
The visitors will be without midfielder Benjamin Andre after the 23-year-old was sent off in stoppage time at the Stade Francois Coty last week, but Blanc has concerns of his own.
Seven PSG players represented their countries in mid-week friendlies and they will need to be assessed ahead of the game, with the likes of Zlatan Ibrahimovic, captain Thiago Silva and Argentina international Ezequiel Lavezzi facing fitness tests.
New signing Edinson Cavani - who arrived from Napoli for a fee of around €64million last month - is also set to feature for his home debut, with Blanc confirming his availabilty prior to the match.
"Certainly. But the question is will he start?" he said when asked if the Uruguay international is in line for selection.
"That is a decision we will take. He is a little bit behind with his preparation and has had some fitness problems."
Ajaccio's major close-season recruit, midfielder Benoit Pedretti, is sure to be among Ravanelli's starting XI as they look for a repeat of last season's encounter at the Parc des Princes, when they held PSG to a 0-0 draw.