Horwill was named among the replacements for last Saturday's 60-11 thrashing of the invitational Barbarians side at Twickenham with openside flank David Pocock leading the team.
However, the Reds lock returns as skipper after a two-try, 30 minute cameo last weekend with Nathan Sharpe dropping to the replacements bench.
Centre Ben Tapuai and utility back Ben Lucas will both be optimistic of making their test debuts after being named alongside Sharpe on the bench.
Utility back James O'Connor continues at flyhalf after an impressive display against the Barbarians with inside centre Berrick Barnes recovering from a blow to his back to maintain the continuity in the backline.
Australia won the recent Auckland encounter 21-18 but Deans warned that Warren Gatland's Wales team would be fired up for the encounter ahead of the Six Nations starting in February.
"Warren will be looking for his group to push on from the World Cup and this match provides him with a perfect opportunity to do just that as a springboard heading into the next Six Nations," Deans said in a statement.
Sharpe won his 100th cap in the World Cup contest at Eden Park and Deans said that Wales would be buoyed by a similar emotional edge as the match in Cardiff is to be a final farewell to international rugby for Wales winger Shane Williams.
"We experienced ourselves how powerful the additional motivation of playing for a mate can be, when 'Sharpie' had his 100th Test in Auckland," Deans said.
"There was no way any of the other players wanted to let him down. I've no doubts that the Welsh lads will be feeling just the same this week as we did in Auckland. Emotion plays a powerful role in competitive sport."
Teams:
Australia:
15 Adam Ashley-Cooper, 14 Lachie Turner, 13 Rob Horne, 12 Berrick Barnes, 11 Digby Ioane, 10 James O'Connor, 9 Will Genia, 8 Ben McCalman, 7 David Pocock, 6 Scott Higginbotham, 5 Rob Simmons, 4 James Horwill, 3 Salesi Ma'afu, 2 Tatafu Polota Nau, 1 James Slipper.
Substitutes: 16 Stephen Moore, 17 Ben Alexander, 18 Nathan Sharpe, 19 Radike Samo, 20 Ben Lucas, 21 Ben Tapuai, 22 Anthony Fainga'a
Wales:
15 Leigh Halfpenny, 14 George North, 13 Scott Williams, 12 Jamie Roberts, 11 Shane Williams, 10 Rhys Priestland, 9 Lloyd Williams, 8 Toby Faletua, 7 Sam Warburton (captain), 6 Dan Lydiate, 5 Ian Evans, 4 Bradley Davies, 3 Scott Andrews, 2 Huw Bennett, 1 Gethin Jenkins
Substitutes: 16 Matthew Rees, 17 Ryan Bevington, 18 Ryan Jones, 19 Justin Tipuric, 20 Tavis Knoyle, 21 Dan Biggar, 22 Alex Cuthbert