It is important for programmers(and other anal types) that, although Ctrl+Esc and WinKey cause the same action in Windows (make the Start Menu open), they do not "do" the same thing, strictly speaking. As 'xev' told me, the WinKey's scancode is 115, while Ctrl+Esc is 37+9.
This is somewhat useful because for the longest time I thought that the Windows Key was simply a hardware alias to Ctrl+Esc -- I know now that it is most certainly not.