Kaymer also won the 2010 PGA Championship, while McIlroy is the reigning Open Championship and PGA Championship winner. The duo will be joined by U.S. Amateur champ Gunn Yang on the 10th tee at 11:28 a.m. ET on Thursday. They go off the first at 5:28 p.m. on Friday.
Six-time runner-up Phil Mickelson will play alongside 2007 titlist Angel Cabrera and two-time Masters winner Bubba Watson. That trio starts on the first tee at 10:33 a.m. Thursday and goes off the 10th at 4:33 p.m. on Friday.
Tiger Woods, a three-time U.S. Open winner, will play alongside Rickie Fowler and 2010 Open Champion Louis Oosthuizen for the first two rounds. They will open the year's second major on the first tee Thursday at 5:28 p.m. and come back Friday at 11:28 a.m. Friday.
Immediately preceding that trio will be Masters champion Jordan Spieth, 2013 U.S. Open winner Justin Rose and Jason Day, who has twice been a runner-up at the U.S. Open.
The following group has 2003 winner Jim Furyk, reigning U.S. Senior Open champ Colin Montgomerie and Miguel Angel Jimenez. Next up is Brooks Koepka, Russell Henley and former U.S. Amateur winner Byeong-Hun An.
Early players on the back nine Thursday include 2010 champ Graeme McDowell playing with Hideki Matsuyama and Matt Kuchar at 11:06 a.m. The next group, which precedes Kaymer and McIlroy, will be Sergio Garcia, 2013 Masters winner Adam Scott and Dustin Johnson, who led entering the final round in 2010 at Pebble Beach.
Patrick Reed, 2012 champ Webb Simpson and 2011 PGA Championship winner Keegan Bradley are among the players in the groups right after Kaymer and McIlroy.
Ryo Ishikawa, Luke Donald and J.B. Holmes start at 4:22 p.m. on Thursday on the 10th tee. Five groups later will be reigning FedExCup champ Billy Horschel alongside Englishmen Paul Casey and Lee Westwood.