PC Stats has published a beginners guides about Cloning WindowsXP

If you upgrade your operating system hard disk, chances are the new one will be both faster and larger than your original disk. Since you can have multiple drives in your system, it makes sense to keep WindowsXP on the fastest drive, since its speed will make the most difference in that configuration. Trouble is, WindowsXP can't just be copied over from your old drive to the new one. There are essential files which will not be created on the new disk if you try this. So what to do? Follow along as we walk you through an easy process to simplify your life, so you can get back to work.

Beginners Guides: Cloning WindowsXP