American club professional Rob Labritz found the right side of the fairway with the opening shot at the par-four first, before being followed by Australian John Senden and Ireland's Shane Lowry.
Americans Charley Hoffman, Bob Sowards and Matt Every launched proceedings at the par-four 10th hole on the heavily tree-lined East Course at Oak Hill Country Club.
Woods, who clinched the most recent of his PGA Championship titles in 2007, was scheduled to start his opening round from the 10th at 8:35 a.m. ET (1235 GMT) on a course softened by two inches of rain overnight.
The American, hunting his 15th major crown but first since the 2008 U.S. Open, has been grouped with former champions Keegan Bradley and Davis Love III for the first two rounds.
In keeping with tradition, this season's first three major winners have been grouped together - Australian Adam Scott (Masters), Englishman Justin Rose (U.S. Open) and American Phil Mickelson (British Open).
Scott and company were set to start on the first tee from 1:45 p.m.
In other high-profile groups, Northern Ireland's Graeme McDowell, South African Ernie Els and American Bill Haas will play together while 2012 Masters champion Bubba Watson of the U.S. has been drawn with South African Tim Clark and England's Lee Westwood.
Northern Ireland's defending champion Rory McIlroy, seeking to turn his game around after a poor year by his standards, will set off in the company of former winners Vijay Singh of Fiji (1998) and Germany's Martin Kaymer (2010).
Shaun Micheel, who won the most recent PGA Championship played at Oak Hill in 2003, has been paired with fellow Americans Rich Beem and Mark Brooks, both former winners.
The PGA Championship has, in recent years, enjoyed the strongest field of the four majors and 99 of the world's top 100 players are chasing the season's final grand slam title this week.
Weather forecasts predicted a slight chance of thunderstorms on Thursday with conditions expected to become mainly sunny during the afternoon.
(Reporting by Mark Lamport-Stokes; Editing by Frank Pingue)
