The 53-year-old has been handed the ceremonial honour, which will televised live for the first time, by the R&A after qualifying for the Claret Jug event for the first time since 2010.
Montgomerie will tee off at 6.35am in the first round along with Australian Marc Leishman, one of the players who lost out to Zach Johnson, in a play-off at St Andrews 12 months ago.
Making up the opening group is England’s former world No 1 Luke Donald, who came off the reserve list last week to earn his place in the field.
Scottish No 1 Russell Knox will also find himself in the spotlight on the opening two days in Ayrshire afrer being paired with US Open champion Dustin Johnson and two-time major winner Martin Kaymer.
World No 1 Jason Day will have Masters champion Danny Willett and 2015 Scottish Open champion Rickie Fowler for company for the first two days.
Third-ranked Jordan Spieth is out with Justin Rose and Shane Lowry while four-time major winner Rory McIlroy is out with Hideki Matsuyama and Bubba Watson.
Selected first-round tee times
06.35 : Colin Montgomerie, Marc Leishman, Luke Donald.
07.19 : Richie Ramsay, Danny Lee, Harris English.
07.41 : Darren Clarke, Thorbjorn Olesen, Jim Furyk.
08.14 : Paul Lawrie, Brandt Snedeker, Thongchai Jaidee.
08.25 : Padraig Harrington, Louis Oosthuizen, Jamie Donalson.
09.00 : Jordan Spieth, Justin Rose, Shane Lowry.
09.25 : Danny Willet, Rickie Fowler, Jason Day.
09.36 : Rory McIlroy, Hideki Matsuyama, Bubba Watson.
12.31 : Todd Hamilton, Justin Leonard, Marc Calcavechia.
1.15 : Graeme McDowell, Matt Kuchar, Andrew Johnston.
1.26 : Phil Mickelson, Lee Westwood, Ernie Els.
2.04 : Dustin Johnson, Martin Kaymer, Russell Knox.
2.15 : Zach Johnson, Adam Scott, Henrik Stenson.
2.37 : Miguel Angel Jimenez, Jason Dufner, Marc Warren.
2.48 : Anirban Lahiri, Sergio Garcia, Keegan Bradley.