Naming Sergio Garcia in such a role has already been universally acclaimed as a fine idea, such is the 30-year-old Spaniard's love and affinity for this competition. Garcia's modern form has been woeful enough to preclude his consideration in a playing capacity, but no one can forget the passion and productivity he brought to the European challenge on countless occasions.
Surely Montgomerie had his mind's eye trained upon the memory of another Spaniard, Seve Ballesteros, and his inspirational captaincy role at Valderrama in 1997, when scratching in Garcia's name.
Montgomerie is an often irascible character whose mood swings can be just as dark as his golf swing, at least in his prime, was glorious.
The Ryder Cup, and the chance to square off against the United States, always brought out his finest as a player and there is great hope in Europe that he can have a similar effect in a managerial role.
His preparations have been lengthy and meticulous, and Sunday provided the chance to make the first of an endless stream of decisions that will determine whether the trophy is retained by the United States or is wrested back by Europe.
Montgomerie's trio of captain's picks - Padraig Harrington, Luke Donald and Edoardo Molinari - represent either bravery or foolhardiness, but it won't be until late in the evening of October 3 that we know which.
In making his picks, the Europe captain juggled the various facets of championship-winning experience, public profile, ranking status and fresh-faced enthusiasm yet was plagued by the reality that five doesn't go into three. Harrington got the nod as he is Europe's only multiple major winner, Donald for past Ryder Cup consistency, Molinari for the sparkling recent form that saw him win Sunday's Johnnie Walker Championship with three birdies in the last three holes.
For Paul Casey (ninth in the world) and Justin Rose (No.22), ranking and recognition were not enough. For those men, the certainty that their absence will be used as a stick to beat Montgomerie with should Europe fail, will be little consolation.
Montgomerie knows full well that there is no such thing as an honorable defeat in the Ryder Cup, the only event in mainstream sports where traditional rivalries between European nations are set aside and the continent unites behind a common goal.
As such, he is leaving nothing to chance, so much so that he has even appointed a local Welshman, Rhys Davies, as his personal buggy driver for the event.
Davies, an emerging talent who won a European Tour event earlier this year, knows the Celtic Manor course "like the back of his hand" and will surely be able to offer some useful insight as well as driving skills.
Just another of the little extras that can't be measured by strokes or yardage.
"Of course this is going to be decided on the course," said Montgomerie. "But there are a thousand other things that you can do. If even a few of those things give your team a fractional edge, it could make all the difference."