Shaun Connor (hamstring) will be monitored after missing the Quins tie, while Matthew Jones, Craig Mitchell and Tim Evans remain long-term injuries.
Hook, 21, impressed on the senior Wales tour to Argentina this summer and has an early chance to make the Ospreys number 10 jersey his own.
If the youngster lacks experience then his half-back partner, former New Zealand scrum-half Justin Marshall, has more than enough for both of them.
Ospreys coach Lyn Jones said: "Edinburgh have played well and looked a strong side in their pre-season fixtures.
"They are a confident group of players following their performances in the Celtic League and Six Nations last season.
"Having said that we will be looking to concentrate on our own performance.
"Although we still do not expect to be firing on all cylinders, we hope that the quality of our individuals will pull us through."
Wales full-back Lee Byrne, a summer recruit from Llanelli Scarlets, starts along with fellow former Scarlet Tal Selley, who gets the nod on the wing over another new recruit, Nikki Walker.
Ospreys trio David Bishop (knee), Richard Pugh (knee) and Cai Griffiths (shoulder) could return against Ulster (22 Sept).
Scrum-half Jason Spice is also expected back for that fixture after his spell with Wellington.
Ian Evans is currently suspended, but his ban will be over in time for the lock to face Cardiff Blues (13 September).
Ospreys: Lee Byrne; Tal Selley, Sonny Parker, Gavin Henson, Shane Williams; James Hook, Justin Marshall; Duncan Jones (capt), Huw Bennett, Adam Jones, Brent Cockbain, Alun-Wyn Jones, Jonathan Thomas, Steve Tandy, Ryan Jones.
Replacements: Richard Hibbard, Paul James Lyndon Bateman, Filo Tiatia, Martin Roberts, Andrew Bishop, Nikki Walker.