Wales prop Gethin Jenkins is out of the Six Nations match against England on Saturday with a calf injury.
Paul James takes his place at loose-head, with uncapped Rhys Gill coming onto the bench for the Twickenham game.
The news follows the loss of Jenkins' British & Irish Lions team-mate Matthew Rees to a calf injury - the hooker's place taken by Gareth Williams.
Tom James is selected on the right wing ahead of Leigh Halfpenny, with James Hook alongside Jamie Roberts at centre.
Lee Byrne's availability after his ban was overturned allowed Wales to name a new-look back line, with Hook moving up from full-back.
Gareth Cooper wins the scrum-half berth ahead of Richie Rees, while Luke Charteris retains his spot at lock.
Captain Ryan Jones remains in his favoured number eight berth, with Andy Powell staying at blind-side flanker.
Fit-again tight-head prop Adam Jones returns to the side having missed the autumn Tests with a shoulder injury.
Lions wing Halfpenny has to settle for a place on the bench, alongside the uncapped Rees.
Rees is first-choice scrum-half at the Blues ahead of Cooper, but his more experienced team-mate gets the Wales nod, in the injury-enforced absence of Dwayne Peel and Mike Phillips.
"Paul James has been one of the form props in the Welsh regions so far this season and we are confident he will be a more than able deputy for Gethin," said Wales coach Warren Gatland, after it was revealed that Jenkins had picked up an injury in training.
"Obviously it's not ideal for us to lose Gethin at this stage and we wish him a speedy recovery."
Jenkins will remain in the Wales camp and his injury will be re-assessed next week.
Gatland had delayed naming his team for Saturday's Twickenham showdown as he was waiting for Byrne's appeal against a two-match ban he received for his part in the Ospreys having 16 men on the field for a short time during last month's Heineken Cup win over Leicester.
The Lions full-back, who missed the autumn Tests with a foot injury, was cleared by a European Rugby Cup hearing on Tuesday.
Hook deputised for Wales at 15 in November, but after the 12-33 home hammering against Australia that closed the series the Wales camp was united in stressing that they would go back to the drawing board with their game plan.
More kicking, an increased emphasis on competing for the ball in the air, an extra creative spark in midfield and more pressure at the tackle area were the stated areas to concentrate on.
Byrne's siege-gun boot will boost the kicking game, while Lions man-of-the-series Roberts returns to his favoured inside centre position, having laboured at 13 in the autumn.
Hook, who has stated that his favourite position is fly-half, has not played at outside centre for Wales before and his last start at 12 was in the World Cup defeat to Fiji in 2007.
But he has been in impressive midfield form for the Ospreys and he could fill the creative void that has been missing in Gavin Henson's continued absence.
"James has the skill set to play in a variety of positions and you sometimes feel like you just have to find a role for him, but we think we may have found his position," said Wales attack coach Rob Howley.
Eight-cap Blues hooker Williams, 31, has sometimes been regarded as too small for international rugby, but he impressed the Wales management on last summer's tour of North America.
"Gareth Williams has been in great form for his region and produced some impressive performances in recent weeks and very much deserves his chance," said Gatland, who will give the 5ft 6ins Bridgend man his third Test start.
"We are obviously disappointed for Matthew but he returned to us with a sore groin after playing at the weekend and he has not responded as quickly as we would have like to treatment.
"Gareth is surrounded by a wealth of experience not just in the front row but throughout the forwards.
"We have a pretty settled pack at the moment with our captain playing particularly well and Andy Powell settling into the blind-side role with some great performances for the Blues.
"Andy is looking comfortable there, in his last couple of performances for the Blues he has been error free and very strong and we are looking for him to keep that up at international level.
"It's a big game for the second rows not just because of the standard of the opposition we are up against but also because we have a number of players competing for a starting spot.
"We are looking for the likes of Luke Charteris to really nail his performance."
Wales team to face England: Lee Byrne (Ospreys); Tom James (Blues), James Hook (Ospreys), Jamie Roberts (Blues), Shane Williams (Ospreys); Stephen Jones (Scarlets); Gareth Cooper (Blues); Paul James (Ospreys), Gareth Williams (Blues), Adam Jones (Ospreys), Alun Wyn Jones (Ospreys), Luke Charteris (Dragons), Andy Powell (Blues), Martyn Williams (Blues), Ryan Jones (Ospreys, capt).
Replacements: Huw Bennett (Ospreys), Rhys Gill (Saracens), Bradley Davies (Blues), Jonathan Thomas (Ospreys), Richie Rees (Blues), Andrew Bishop (Ospreys), Leigh Halfpenny (Blues).
Wales' 35-man Six Nations squad:
Backs: Gareth Cooper, Leigh Halfpenny, Tom James, Richard Rees, Jamie Roberts, Tom Shanklin (all Cardiff Blues) Dan Biggar, Andrew Bishop, Lee Byrne, James Hook, Kristian Phillips, Tom Prydie, Shane Williams (all Ospreys), Jonathan Davies, Stephen Jones, Martin Roberts (all Scarlets).
Forwards: Bradley Davies, Gethin Jenkins, Deiniol Jones, Andy Powell, Sam Warburton, Gareth Williams, Martyn Williams (all Cardiff Blues), Huw Bennett, Ian Gough, Paul James, Adam Jones, Alun-Wyn Jones, Ryan Jones, Jonathan Thomas (all Ospreys), Matthew Rees (Scarlets), Luke Charteris, Dan Lydiate (both Newport Gwent Dragons), Eifion Lewis-Roberts (Sale Sharks), Rhys Gill (Saracens).