As others have already pointed out, probably not a good idea. If you still insist then
you could try to edit /etc/passwd manually and change root's entry from:
Code:
root:x:0:0::/root:/bin/bash
to
Code:
root:x:0:0::/var/www:/bin/bash
Afterwards logout and log back in again. I have not tried it myself so I do not know if it will work. Let us know how it goes.
Update
I just tried in inside a container and it worked! I manually changed root's home directory to /var and after I logged out and back in I was in /var.
When I first read the thread my initial thought was that root's home might be hard coded. As it seems you can choose it to be something else. Still not sure why anyone would want to do that.