Although it has never done so, the Electoral College could, indeed, do as you say, but to date there haven't even been a whole lot of instances of individual Electors bolting, let alone an en-masse event.
Lack of consideration of subverting the "democratic process" via the charter documents of the democracy might well be due to ignorance. I'd venture to say that at least 95% of Americans (and 99.99% of the rest of the world's population) have no clue about the formation of the Electoral College or its mandate and potential powers. One can only dream ....
