England's Chris Wood, and Americans Mark O'Meara and Ryan Moore will be the first group away at 06:35 BST.
Following them is reigning champion Henrik Stenson, American sensation Jordan Spieth and Players victor Si Woo Kim at 9.47am. "We certainly need to step that up quite a lot if we want to have anything to do with it next week". There's always a chance and I'm going to enjoy the week.
"I know I'm not really where I want to be in my game and maybe nothing else, either", Stenson said, "but I'll try to enjoy".
The final group available begin at 9.58am and contains Justin Rose, Justin Thomas and 2010 champion Louis Oosthuizen, with voting closing at midday on Wednesday.
Another eye-catching pairing features current world number one Dustin Johnson playing alongside Rory McIlroy.
Belgium's Ryder Cup hero Thomas Pieters and Padraig Harrington, who successfully defended his Open crown at Birkdale in 2008, kick-start their bid for glory at 9.36am.
Local favourite Tommy Fleetwood, who was fourth in the US Open behind Brooks Koepka, will renew battle with the American at 10:09am along with Japan's Hideki Matsuyama, who was joint second at Erin Hills.
Other notable groups include: Zach Johnson, Sergio Garcia and and Jason Day (8:04 a.m. ET); Rickie Fowler, Adam Scott and Paul Casey (8:26 a.m. ET); Rory McIlroy, Dustin Johnson and Charl Schwartzel (9:48 a.m. ET); Jon Rahm, Patrick Reed and Lee Westwood (9:59 a.m. ET) and Phil Mickelson, Franceso Molinary and Marc Leishman (10:10 a.m. ET).