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.
Open from the air
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.
ROB HODGETTS BLOG
“Entering the course, you pass a row of pictures bringing to life the late, great Seve Ballesteros' air-punching Open celebration in 1984”
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