It's also a kinda crappy alternative, because it's not possible on a large number of non-English keyboard. Ctrl+c is also an option, although I think there's a slight difference.
ESC is 0x1B, traditionally the CTRL key reset the two highest bit of the ASCII code, [ is 0x5B, if you reset the two highest bits of 0x5B you get 0x1B which is why ESC and CTRL-[ are the same thing.
I wonder how many vim users have tried using CTRL + [ for the first time today. Muscle memory being what it is I fully expect that nobody will swap over to this new and improved Apple way of pressing the Escape key.
And vi too - works just fine, but you have a valid point about muscle memory, which is pretty much the only kind of memory many of us have left when it comes to vi-like editors, since the key sequences disappeared from our brains decades ago!