For instance, the entry for I begins as follows: "I is the first letter of the alphabet, the first word of the language, the first thought of the mind, the first object of affection." Despite this, the letter I, even though it is the "first letter of the alphabet", is still placed where one would expect—as the ninth letter. Bierce gives a similar treatment to the letter X:
"X in our alphabet being a needless letter has an added invincibility to the attacks of the spelling reformers, and like them, will doubtless last as long as the language. ... Words beginning with X are Grecian and will not be defined in this standard English dictionary."
Here, X's normal place in the alphabet is not only questioned, as it is with I's, but rejected outright. Yet its very inclusion in the dictionary—and, once again, in its "proper" place as the twenty-fourth letter—conflicts with that stance.
Ironically, Bierce did write an entry on A, what he calls "the first letter in every properly constructed alphabet." However, it was left out of the original publication of The Devil's Dictionary, as Ernest J. Hopkins notes in his edition of The Enlarged Devil's Dictionary, and the entry is not included in many recent editions.
The Devil's Dictionary does not define even a rudimentary vocabulary, only words which struck Bierce's fancy over the years. So with no way to predict which words are included in the dictionary, no one will be "looking up" words in it, unless the reader is looking for an entry with which he or she is already familiar. Even so, a thematic arrangement could serve just as well, assuming convenience is an objective.
The entry on the letter I, for example, could indeed have been the first in the book, or the entry on X, the last (even as appendix or apocrypha): it would make no difference to the dictionary's "usefulness."
That the letter I is where it is says something about the lingering power of alphabetical order. The entries could have been listed in reverse (though this would still assume knowledge of an alphabetical order), or merely jumbled. But without expectations to rail against, satire loses its focus; without juxtaposition, irony is lost.
If anyone knew this, it was "Bitter" Bierce. He likely didn't consider as targets for his satire kabbalistic ideas—that the alphabet represents the elements of the universe, or that the alphabet is a divinely inspired gift to man—but Bierce understood the over-reliance those "grammarians" he mocks in his dictionary placed on the arbitrary rules of the alphabet.
After all, if anyone's dictionary would arrange itself to undermine such an alphabetic order, whose would it be if not the Devil's?