It depends. XP can only access MBR disks and MBR is limited to 2TB. However some 3TB external drives contain some low level sector emulation that allows XP to read the 3TB out of the box. You'll need to check reviews/manufacturer spec sheets on a drive by drive basis to find a suitable one.
I know this is slightly off topic but have you considered installing Windows 7? Its a far better operating system and will work perfectly with a 3TB external drive.
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