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If you're going to use Bootcamp, I'd go with 7, even if theres some legacy software that is supported by XP at the latest, Windows 7 Business & Ultimate come with a feature called 'XP Mode' where you can emulate 1 Windows XP program on your Windows 7 desktop, or you can use the built-in XP Mode Virtual Client.

I know you could just parellel XP, It's best to just Bootcamp 7 I'd say, that way you get the latest things that are designed for the features in 7, with XP support too.
 
Both

1. Windows 7 should be primary as you're installing a very good 64bit system that's all ready for the future... and install it natively on a Bootcamp partition - beware that it steals about 20GB hard drive space though (I haven't found it too heavy on ram).

2. Install Windows XP (if you've already got the licence, may as well keep it!) via virtualisation, and use it to run older programs.

3. Get Parallels 5 to access both in virtualisation (one time process: after installing Parallels Tools on the Bootcamp partition, you'll need to go back natively to reinstall the bootcamp drivers over the top - you'll need a snow leopard disk or to get the bootcamp update download from apple)

You can run all the latest 64bit Windows stuff on Win7, and use WinXP for things like Office 2003 (most business are still running <2007, and I need to ensure they see things on their screen as I do on mine - most of the time 2007-2003 disagree!).
 
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