Both teams spent heavily in the off-season with Qatari-backed PSG going cheque-book to cheque-book against the Russian-backed Principality outfit in a billionaires' battle for the game's most coveted players.
PSG coach Laurent Blanc welcomed Uruguay international Edinson Cavani from Napoli where he was Italy's top scorer last season, in the sixth highest transfer deal of all time at some €64m.
While Monaco stunned the European football world when they captured the highly-rated Colombian Radamel Falcao for €60m from Atletico Madrid.
Falcao was not the only recruit brought in by Italian coach Claudio Ranieri who also splashed out on big money deals to bring in James Rodriguez, Joao Moutinho and Geoffrey Kondogbia, while captain Eric Abidal was picked up on a free from Barcelona.
Both teams are off to unbeaten starts although Monaco come into the match one point clear of Saint-Etienne while PSG are two points back but starting to change gears after an eye-catching 4-1 win over Olympiacos in midweek gave their UEFA Champions League quest a dream start.
"Obviously we are getting stronger and physically we have taken it to a higher level now," Blanc, the former Bordeaux and France coach, said.
"We are going to prepare meticulously for this match against a very good team in very good form," added the 47-year-old
Thiago Motta, who scored twice in Athens, feels the team is still a work in progress despite winning their first French title since 1994 last season.
"We have everything we need to be better and we have the players. It only depends on us now," explained the Brazilian.
League Cup holders Saint-Etienne may profit from their UEFA Europa League elimination as they try to keep pace with the favoured giants when they open the weekend slate at home against second-from-bottom Toulouse on Friday.
Last season's runners-up Marseille are also waiting in the wings and feeling the effects of not having the same financial clout as their rivals, but go into their away match against Bastia lying fourth and only three points off the pace.
Elsewhere, in a battle of former multiple champions, Lyon will try to get their campaign back on track at home to Nantes with both sides marooned in mid-table.
Seven-time title winners Lyon are still reeling from their Champions League elimination and have already lost twice in five league outings as they await the promoted 'Canaries' at the Stade Gerland.
Fifth-placed Rennes host Fabrizio Ravanelli's winless Ajaccio side, Evian await Montpellier and Sochaux are at home to Lille on Saturday.
Bordeaux, who won the 2009 league crown under Blanc, are away to Lorient in a Sunday afternoon fixture between struggling teams trapped in the lower half of the table.
Ligue 1 fixtures
Saint-Etienne v Toulouse
Bastia v Marseille
Evian v Montpellier
Reims v Guingamp
Rennes v Ajaccio
Sochaux v Lille
Lorient v Bordeaux
Lyon v Nantes
Paris Saint-Germain v Monaco