US Open winner Rory McIlroy will play alongside Ernie Els and rising American star Rickie Fowler in the opening round of the 140th Open on Thursday.
Defending champion Louis Oosthuizen has been drawn with Phil Mickelson and US PGA champion Martin Kaymer.
World number one and Scottish Open champion Luke Donald plays with Spain's Sergio Garcia and Japan's Ryo Ishikawa.
Lee Westwood is paired with Masters champion Charl Schwartzel and American Steve Stricker at Royal St George's.
McIlroy, bidding to become the youngest Open champion since 1893, will tee off at 0909 BST.
The 22-year-old from Northern Ireland is likely to start as favourite after his stunning US Open triumph at Congressional in June but has not played a competitive round since his first major success.
But he will take heart from last year when he hit a score of 63 in the opening round to set a record for the lowest ever score in the first round of the Open.
American Jerry Kelly will hit the first shot of this year's event at 0630 BST.
Donald goes out in the group immediately after McIlroy, while fellow Englishman Westwood, third and second in the last two Opens, tees off at 1410 BST.
British amateur Tom Lewis, from the same Welwyn Garden City club that launched the career of three-time winner Sir Nick Faldo, is out at 1432 BST with five-time champion Tom Watson and Sweden's Henrik Stenson.
Colin Montgomerie failed in his bid to qualify at the Scottish Open, missing the tournament for the first time since 1989, while Tiger Woods is injured.
Oosthuizen, a rank outsider at last year's championship, recorded a shock seven-shot victory at St Andrews to claim his first major title.
The 28-year-old South African missed the cut at last week's John Deere Classic as well as the Masters in April but finished joint ninth at the US Open.
See the full list of tee-off times for the first two rounds of the Open here.
BBC Radio 5 live will have a special preview programme at 1900 BST on Wednesday.
Watch BBC Sport's Open preview on BBC Two and online at 2320 BST on Wednesday.