Walker will compete in an official PGA Tour event for the first time since the US Open in June, and should be confident of a strong showing having finished tied for second last year.
Having missed the cut by four shots at The Old White TPC in 2012, Walker sat second heading into the final round of last year's Greenbrier Classic, only to shoot a one-over 71 and miss out on victory by two strokes.
Walker finished in a tie for ninth at the US Open, while the 35-year-old American has won three PGA Tour events this year - the Frys.com Open, Sony Open in Hawaii and AT&T Pebble Beach Pro-Am - and has another five top-10 finishes to his name.
Having played 19 events in America's premier golf tour, Walker leads the FedExCup standings with 2322 points, 239 ahead of second-placed Bubba Watson, who will also be in West Virginia, while Matt Kuchar (1725) sits third.
Watson will tee off on Thursday on the back of a T31 finish in the Travelers Championship, while he missed the cut at the US Open.
The Masters champion has won two tournaments this year with his victory at the Northern Trust Open preceding his triumph at Augusta.
A win in West Virginia for Watson would be enough for the 35-year-old to overhaul Walker in the FedExCup standings.
Other FedExCup top 10 players in action include Chris Kirk, Patrick Reed and Brendon Todd.
Ted Potter Jr will return to the scene of his greatest-ever golf result with the 30-year-old American having overcome Troy Kelly in a three-hole play-off to win at The Old White in 2012.
Potter Jr claimed his only PGA Tour title in White Sulphur Springs, and backed it up with a T6 finish last year.
Defending champion Jonas Blixt will start this year's edition having missed the cut in five of his past seven PGA Tour starts, although he did finish tied for second at the Masters in that period.