The 53-year-old Scot, who had to pre-qualify for the third major championship of the year, will tee off at 0635 local time in the opening round after being paired in Monday's draw with Australian Marc Leishman and England's Luke Donald.
Eight-times European number one Montgomerie, renowned as one of the finest golfers never to win a major on the main tour, is playing at the Open for the first time in six years.
World number one Jason Day launches his campaign at 0925 alongside American Rickie Fowler and England's Danny Willett, the U.S. Masters champion.
Second-ranked Dustin Johnson, the hottest player in the game after winning last month's U.S. Open and the WGC-Bridgestone Invitational in Ohio eight days ago, tees off at 1404 with German Martin Kaymer and Russell Knox of Scotland.
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Third-ranked Jordan Spieth will have England's Justin Rose and Shane Lowry of Ireland for company when he starts at 0903 on Thursday.
World number four Rory McIlroy plays alongside big-hitting American Bubba Watson and Japan's Hideki Matsuyama at 0936.
"It's great to have the honour of hitting the very first shot at your own course," Montgomerie told reporters.
"Everything that happens after that first shot is a bonus and I'm looking forward to walking the fairways and looking forward to the week ahead."
Montgomerie, who now plays regularly on the over-50s seniors circuit, said his dream this week was simply to make the halfway cut.
"There's no pressure on me any more," he added. "I used to put pressure on myself when I was number two in the world and expectations were high.
"My goal this week is to attempt to walk down the 18th fairway on Sunday. Anything beyond that would be a bonus."
(Editing by Rex Gowar)
