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Promising Italian teenager Matteo Manassero will also tee up after suffering a scare when hit by a stray golf ball.
Montgomerie has calf muscle and Achilles tendon damage and the 47-year-old Briton will rely on painkilling injections to play.
The Scot is also fighting to be fit for next week's Scottish Open and the following week's British Open at St Andrews where he hopes to make his 21st consecutive appearance in the major.
Manassero was struck on the left hand by a ball while practising at this week's host National club.
However, the 17-year-old awoke to find swelling and pain in the injury had lessened enough for him to play.
Wednesday's other pro-am casualties, Britons Lee Westwood and Ian Poulter, were set to tee off later on Thursday.
World number three Westwood decided to play after swelling on his calf and ankle, at first thought to be a blood clot, had reduced considerably.
Poulter, suffering a reaction from an insect sting, was to make a late decision.
