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I had this saved from an email I had to write about Outlook yesterday which gives a break down of the differences. Currently, there are two plug-ins available that work with Outlook:
"Connect for Outlook" which requires Microsoft Windows 2000, XP, Vista, or 7 (32-bit only). Also, it requires Microsoft Outlook XP (2002), 2003 or 2007
"Salesforce for Outlook" which required Microsoft Windows 7 (64-bit and 32-bit), Vista (32-bit only), XP (32-bit only). Also it requires Microsoft Outlook 2010 (64-bit and 32-bit) or 2007.
With this knowledge if you have a 64-bit os you'll need Outlook 07 or 10. Myself I have a 64-bit processer computer but run standard 32-bit XP with Office 03 and it runs fine. So it's not so much that if you have a 64-bit capable PC, it is are you running 64-bit programs?