Former Ilkley member Montgomerie, who is making his first appearance in the Open since 2010 after coming through final qualifying, tees off at 6.35am alongside former world No 1 Luke Donald and Australia’s Marc Leishman.
The 53-year-old, whose father James was club secretary for more than 20 years and will soon take over as president, finished 24th and 25th respectively the last time Troon staged the Open in 1997 and 2004.
Speaking ahead of last week’s Scottish Open, Montgomerie said he would probably not have entered the 36-hole qualifying event if the Open had not been at Troon.
“Because it was Royal Troon I thought I’ll give it a go and it was quite a big deal to qualify,” the former European No 1 said. “
“It was more of a relief than anything because I’d come so close at Sunningdale last year to winning the British Seniors and I knew the winner got an invite into Troon.
“Having qualified, the goal is to be there on Sunday and that has changed, no question. Back in the Nineties, I was going to the Open to win it. That has changed of course. You have to be realistic.’’
World No 3 Jordan Spieth gets his campaign for a third major title under way at 9.03am alongside former US Open champion Justin Rose and Ireland’s Shane Lowry, who let slip a four-shot lead in the final round at Oakmont in the US Open last month.
Masters champion Danny Willett, the Yorkshireman who was sixth last year, tees off at 9.25am with Rickie Fowler and world No 1 Jason Day, who missed out on the three-man play-off at St Andrews 12 months ago by a single shot.
In the group behind, 2014 champion Rory McIlroy – ruled out last year by an ankle injury – will play the first two rounds alongside Japan’s Hideki Matsuyama and two-time Masters winner Bubba Watson.
The last three Open champions at Troon - Todd Hamilton, Justin Leonard and Mark Calcavecchia - tee off together at 12.31pm, with defending champion Zach Johnson, Adam Scott and Henrik Stenson out at 2.15pm.
US Open champion Dustin Johnson gets his bid for back-to-back titles under way 11 minutes earlier alongside Germany’s Martin Kaymer and Scotland’s Russell Knox.
Tee-off times in the first round of the the 145th Open Championship
(Gbr & Irl unless stated):
* denotes amateurs
0635 Marc Leishman (Aus), Colin Montgomerie, Luke Donald
0646Steven Alker (Nzl), Marcus Fraser (Aus), Sang-hee Lee (Kor)
0657 Jeunghun Wang (Kor), Jon Rahm (Spa), Ryan Palmer (USA)
0708 Scott Gregory*, Sandy Lyle, David Duval (USA)
0719 Richie Ramsay, Danny Lee (Nzl), Harris English (USA)
0730 Steven Bowditch (Aus), Alex Noren (Swe), Kevin Chappell (USA)
0741 Thorbjorn Olesen (Den), Darren Clarke, Jim Furyk (USA)
0752 Justin Thomas (USA), David Lingmerth (Swe), Kiradech Aphibarnrat (Tha)
0803 Patrick Reed (USA), Branden Grace (Rsa), Byeong-Hun An (Kor)
0814 Paul Lawrie, Brandt Snedeker (USA), Thongchai Jaidee (Tha)
0825 Padraig Harrington, Louis Oosthuizen (Rsa), Jamie Donaldson
0836 Scott Piercy (USA), Paul Dunne, Jamie Lovemark (USA)
0847 Victor Dubuisson (Fra), Jimmy Walker (USA), Scott Hend (Aus)
0903 Justin Rose, Jordan Spieth (USA), Shane Lowry
0914 Ross Fisher, Steve Stricker (USA), Vijay Singh (Fij)
0925 Danny Willett, Rickie Fowler (USA), Jason Day (Aus)
0936 Hideki Matsuyama (Jpn), Rory McIlroy, Bubba Watson (USA)
0947 Gary Woodland (USA), James Morrison, Soomin Lee (Kor)
0958 Chris Kirk (USA), Smylie Kaufman (USA), George Coetzee (Rsa)
1009 Matthew Fitzpatrick, Billy Horschel (USA), Hideto Tanihara (Jpn)
1020 Matteo Manassero (Ita), Shugo Imahira (Jpn), Russell Henley (USA)
1031 Robert Rock, Kodai Ichihara (Jpn), William McGirt (USA)
1042 Brendan Steele (USA), Richard Sterne (Rsa), Matt Jones (Aus)
1053 Patton Kizzire (USA), Nicolas Colsaerts (Bel), Rod Pampling (Aus)
1104 Dave Coupland, Nathan Holman (Aus), Phachara Khongwatmai (Tha)
1115 Rikard Karlberg (Swe), Scott Fernandez (Spa), Haydn Porteous (Rsa)
1136 Kristoffer Broberg (Swe), Greg Chalmers (Aus), Clement Sordet (Fra)
1147 David Howell, Seung-Yul Noh (Kor), Tony Finau (USA)
1158 Jordan Niebrugge (USA), Nick Cullen (Aus), Robert Streb (USA)
1209 Stefano Mazzoli* (Ita), Ben Curtis (USA), John Daly (USA)
1220 Francesco Molinari (Ita), Kevin Kisner (USA), K.T. Kim (Kor)
1231 Justin Leonard (USA), Todd Hamilton (USA), Mark Calcavecchia (USA)
1242 Lasse Jensen (Den), Soren Kjeldsen (Den), Bill Haas (USA)
1253 Paul Casey, Charl Schwartzel (Rsa), Kevin Na (USA)
1304 Joost Luiten (Ned), Emiliano Grillo (Arg), Charley Hoffman (USA)
1315 Graeme McDowell, Matt Kuchar (USA), Andrew Johnson (USA)
1326 Phil Mickelson (USA), Lee Westwood, Ernie Els (Rsa)
1337 Satoshi Kodaira (Jpn), James Hahn (USA), Andrew Sullivan
1348 Bernd Wiesberger (Aut), Ryan Moore (USA), Tommy Fleetwood
1404 Martin Kaymer (Ger), Dustin Johnson (USA), Russell Knox
1415 Zach Johnson (USA), Adam Scott (Aus), Henrik Stenson (Swe)
1426 Yusaku Miyazato (Jpn), Chris Wood, Mark O’Meara (USA)
1437 Miguel Angel Jimenez (Spa), Jason Dufner (USA), Marc Warren
1448 Anirban Lahiri (Ind), Sergio Garcia (Spa), Keegan Bradley (USA)
1459 Webb Simpson (USA), Yuta Ikeda (Jpn), Thomas Pieters (Bel)
1510 Rafael Cabrera-Bello (Spa), J.B. Holmes (USA), Brandon Stone (Rsa)
1521 Matthew Southgate, Marco Dawson (USA), Yosuke Tsukada (Jpn)
1532 Jack Senior, James Heath, Brian Gay (USA)
1543 Fabian Gomez (Arg), Jim Herman (USA), Anthony Wall
1554 Paul Howard (Gbr), Daniel Summerhays (USA), Colt Knost (USA)
1605 Oskar Arvidsson (Swe), Harold Varner III (USA), Tyrrell Hatton
1616 Ryan Evans, Callum Shinkwin, Zander Lombard (Rsa)