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Not quite the same as virtualization -- consider that you can't make changes to your video settings through the game, and have those changes persist at the next launch. But indeed, copying files like this would allow you to have WoW load a different copy of config.wtf at launch.
I heard that ISBoxer has Config.wtf virtualization. That software sounds really good. I haven't gotten around to trying it out.
If you change your video settings every time (why are you doing this?) you could use a shutdown hotkey to exit and save your changes. The hotkey would cause a script like this to run (sorry untested):
<Command GoByeBye>
<SendPC Local>
<SendLabel w%1%>
<Key lalt F4>
<Wait 2000>
<Open "c:\Users\Public\Games\World of Warcraft\wowdown.bat %1%>
<HotKey Alt Ctrl K>
<GoByeBye 1>
<GoByeBye 2>
<GoByeBye 3>
<GoByeBye 4>
<GoByeBye 5>
where wowdown.bat has a line like
copy c:\Users\Public\Games\"World of Warcraft"\WTF\Config.wtf c:\Users\Public\Games\"World of Warcraft"\WTF\Config%1.wtf
I'm not really advocating a particular method, I'm just suggesting a possible alternative to multiple wow dirs.
-K