I once wrote ":tabnew something.js" in my IM window and sent it before I realized that the wrong window had focus. The person replied with, "bash: :tabnew: command not found." I told him, "I was hoping you were vim, actually".
Also using vim will cause your escape key to be heavily hit constantly after typing anything especially if you are not sure what mode you are in, then only realizing you are not in vim period.
I've found it easy to avoid misusing Ctrl-w because of the fact I use it so much to close tabs in Firefox. You just need to have two different uses for something, both of which you use very regularly, to get used to not accidentally misusing them, I've found.
Alas, I think you may be right. I haven't been using it very long.
Once I actually buckled down and started learning how to use it, I was surprised by how quickly and easily a natural feeling of "this is how it should be" developed while using Vimperator. Of course, there's a lot of positive transference of knowledge from my heavy use of Vim itself, but still -- I didn't expect to find it this easy.
I think part of the reason may be that every single keyboard-driven browser I have ever used before (Lynx, W3m, Links, et cetera, ad infinitum) was so awful as a Web interface that I became convinced Web browsers were a uniquely GUI-suited type of application. Vimperator is definitely changing my mind.
When I first switched to my Mac, when I'd switch between split windows (ctrl w w), I'd often accidentally close my Terminal session (command w). The Apple Command sat where I expected ctrl to be.