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A regular contender for the No. 10 jersey when he first made it into the side, Hook played at fullback in last week's opening defeat to England but switches to flyhalf for the first time in two years after Stephen Jones injured his neck.
"He'll be a threat for us at the weekend, but one that if we put under pressure hopefully that might tell," Scotland scrumhalf Rory Lawson said. "James Hook will be going into the weekend with a lot to prove. We'll look to maybe force his hand in a few areas and put him under pressure."
Hook is a key figure for a Wales side desperate to end a run of eight matches without a win, but Scotland showed promising signs in a 34-21 opening loss to France.
Coach Andy Robinson signed a new contract this week committing him to the Scotland team through the 2015 World Cup, giving his side a huge boost ahead of Saturday's match.
"That continuity is hugely important, his experience is hugely important and it will certainly give the boys a lift," Lawson said.
Robinson may have to replace lock Richie Gray after he sat out training Friday because of a stomach bug. If the 21-year-old Gray is absent, Nathan Hines would likely switch from blindside to the second row, with Kelly Brown moving across to flanker and Richie Vernon coming in off the bench to No. 8.
Robinson also called up Scott MacLeod, with the Edinburgh lock a possible replacement.
"He trained with us today, having also worked with us earlier in the week," Robinson said. "We would have no qualms if he is required tomorrow."
Otherwise, Robinson is hoping to field an unchanged side.
Wales' players are trying to look upon Hook's switch to replace Jones, who scored 11 points but drops to the bench because of his injury, as a positive.
"He has obviously not played 10 too much in the last couple of years with the Ospreys, but personally I think he is a 10," Wales center Jamie Roberts said. "I think he has got the attributes.
"He's a huge running threat in himself. As a center, that makes your job so much easier. It takes a lot of pressure off you when the guy inside you is keeping defenses honest, and James certainly does that."
Hook's switch to flyhalf is one of just three changes to the Wales team beaten 26-19 by England.
Lee Byrne replaces Hook at fullback and Ryan Jones is restored to No. 8 in place of the injured Andy Powell, with coach Warren Gatland opting mostly to give the same players a chance to redeem themselves.
"The forwards were in a battle last week, but there were plenty of things that went right and we want them to go up to Murrayfield and give it a shot," assistant coach Robin McBryde said. "We have talked about better execution and accuracy."
Wales has won seven of its last eight meetings with Scotland, including two of its last three trips to Edinburgh.
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Scotland: Hugo Southwell, Nikki Walker, Joe Ansbro, Nick De Luca, Max Evans, Dan Parks, Rory Lawson; Allan Jacobsen, Ross Ford, Euan Murray, Richie Gray, Alastair Kellock (captain), Nathan Hines, John Barclay, Kelly Brown.
Replacements: Scott Lawson, Moray Low, Richie Vernon, Ross Rennie, Mike Blair, Ruaridh Jackson, Sean Lamont.
Wales: Lee Byrne, Morgan Stoddart, Jamie Roberts, Jonathan Davies, Shane Williams, James Hook, Mike Phillips; Paul James, Matthew Rees (captain), Craig Mitchell, Bradley Davies, Alun-Wyn Jones, Dan Lydiate, Sam Warburton, Ryan Jones.
Replacements: Richard Hibbard, John Yapp, Jonathan Thomas, Josh Turnbull, Tavis Knoyle, Stephen Jones, Rhys Priestland.
