While holding down the [WinKey], (the key with the Windows Logo on it), press the [Pause/Break] key.

Then on the General tab:
  • If you see:
    Microsoft Windows XP
    Professional x64 Edition
    you have the 64-bit version of XP Pro.

  • If you see:
    Microsoft Windows XP
    Professional
    (nothing after the word "Professional"), you have the 32-bit version.