Williams plays in the starting line-up for the first time after just nine minutes of test rugby as blood-bin replacement for Scott Williams against Tonga in June.
The 25-year-old Williams, heralded as a top prospect for Welsh rugby, usually plays at flyhalf for his English club Gloucester but now offers Wales another potential playmaker with Dan Bigger taking the fly half role.
"It will be interesting to see how that goes," said coach Warren Gatland as the team was announced on Thursday.
Josh Navidi replaces injured Justin Tipuric at openside flank while Gareth Davies replaces Rhys Webb, who also did not recover in time for selection, at scrum half.
Navidi and winger Steff Evans are among choices that indicate Gatland's intention to shake up the side as Wales look forward to the 2019 Rugby World Cup.
Alun Wyn Jones captains the side and is one of seven players who went on the Lions tour of New Zealand in mid-year that return to the team, along with Dan Biggar, Jonathan Davies, Taulupe Faletau, Leigh Halfpenny, Ken Owens and Liam Williams.
Wales have three uncapped players – Leon Brown, Sam Cross and Owen Watkin --- on the bench for the first of four tests on successive Saturdays at the Principality Stadium with Georgia (Nov. 18), New Zealand (Nov. 25) and South Africa (Dec. 2) to follow.
"It’s tough start and we have to make sure we are up and running to take on a very competitive Australian team," added Gatland.
Team: 15-Leigh Halfpenny, 14-Liam Williams, 13-Jonathan Davies, 12-Owen Williams, 11-Steff Evans, 10-Dan Biggar, 9-Gareth Davies, 8-Taulupe Faletau, 7-Josh Navidi, 6-Aaron Shingler, 5-Alun Wyn Jones (captain), 4-Jake Ball, 3-Tomas Francis, 2-Ken Owens, 1-Rob Evans
Replacements: 16-Kristian Dacey, 17-Nicky Smith, 18-Leon Brown, 19-Cory Hill 20-Sam Cross, 21-Aled Davies, 22-Owen Watkin, 23-Hallam Amos.
(Reporting by Mark Gleeson; Editing by Toby Davis, William Maclean)
