Sky Sports will have round-the-clock coverage from Royal Birkdale, with a dedicated channel for the 10 days around the third major of the year.
Defending champion Henrik Stenson features in the second trio to consider, with two-time major victor Jordan Spieth and Players champion Si Woo Kim completing that threeball.
Stenson was pessimistic about his chances despite a closing 68 in the Scottish Open on Sunday, after which he was asked if he could emulate Padraig Harrington in winning back-to-back Open titles at Birkdale.
Rickie Fowler, Adam Scott and Paul Casey will play together and Thursday's first group - out at 1:35 a.m. ET - is Mark O'Meara, the Open champion at Birkdale 19 years ago, Chris Wood and Ryan Moore.
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Harrington is in the group ahead of Stenson alongside American Pat Perez and Ryder Cup star Thomas Pieters, with Justin Rose, 2010 victor Louis Oosthuizen and Justin Thomas out at 9:58am.
Pádraig Harrington, who won the Open in 2008 at the Merseyside course, will tee-off alongside Thomas Pieters and Pat Perez at 10.35am while 2011 victor Darren Clarke, who will play alongside Gary Woodland and amateur Harry Ellis, starts his round ten minutes earlier.
US Open champion Brooks Koepka will be looking for back-to-back major successes and will start his quest alongside world number two Hideki Matsuyama and home hopeful Tommy Fleetwood.
Another eye-catching pairing features current world number one Dustin Johnson playing alongside Rory McIlroy.