It is kinda possible I think, but you are really in for a lot of extra work. What you could do is replace the Windows Shell with your own code, but at that point you become solely responsible for the UI that the user interacts with.
If your code isn't 'just right', you may end up with an unusable Windows install, and I'm not sure your users are going to appreciate that much.
Also note that there may be features that you normally intuitively expect to be available on a Windows machine that are part of the shell which you will not have access to anymore. For details, try http://en.wikipedia.org/wiki/Windows_shell_replacement as a starting point.
Addendum:
I have only the vaguest knowledge myself about what is actually involved technically to make this happen, but http://dustyant.com/articles/deeshell/ seems to be a decent explanation of the basics. Again tho... here be dragons make sure you do this in a VM or something so that you don't end up stuffing your main Windows install.
Just briefly what 'Shell Replacement' means: after you log in, windows starts an application called 'explorer' (not sure if this still holds for Vista / Win 7... I have a vague recollection it got a little more involved recently), which basically draws the desktop, the taskbar, etc. ... it is possible to tell Windows to start a different application instead of the default graphical shell. At that point you are in control of the main UI of Windows... which means that you are responsible for everything that Windows normally does in the shell ... gives you a lot of control and flexibility, and possibly lots of headaches.