The full-back was hurt during the 29-17 victory over Italy, having earlier scored a superb solo try.
Hooker Scott Baldwin, meanwhile, is also unavailable for the Stade de France encounter because of a pectoral muscle issue. Ospreys hooker Sam Parry has been called into the squad.
Head coach Warren Gatland will work with a 32-player training group in Nice, where Wales have started preparations to face Les Bleus.
Gatland has options in the full-back position, although Williams' absence is a blow, given his outstanding display at Stadio Olimpico.
Wing Louis Rees-Zammit could be switched, having worn the number 15 shirt during the Autumn Nations Series earlier this season.
And Leigh Halfpenny, who started Wales' 20-10 defeat against England at full-back last month, would also be firmly in the selection frame.
Baldwin, who was among the substitutes in Rome, looks likely to be replaced by Bradley Roberts as bench cover for captain Ken Owens.
The Welsh Rugby Union, meanwhile, added that uncapped Ospreys centre Keiran Williams has been released from the squad.
Williams suffered a groin injury during the Ospreys' United Rugby Championship game against Benetton 10 days ago.
Exeter forward Christ Tshiunza and Cardiff lock Teddy Williams have also been released.
Wales have lost their last four fixtures against France, and will take on a team in buoyant mood following their 53-10 rout of England at Twickenham.
Wales assistant coach Alex King said there were "a few knocks and bruises" after the Italy game, and also praised Liam Williams' performance against the Azzurri.
"I thought he was tremendous on the weekend, so brave," King said, speaking at Wales' team hotel in Nice.
"There were a couple of big moments, especially in the aerial battle, where I thought he really stood up for us.
"We have got some options at 15, and we are looking at those options now. We want to get the balance of the team right for Saturday."