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The easiest way is to place an Outlook shortcut in the Startup folder.
Launch Windows Explorer and navigate to C:\Documents & Settings\All Users\Start Menu\Programs\Microsoft Office\Microsoft Office Outlook 2010.
Right-click Outlook 2010 and select Copy.
Now go to Documents & Settings\All Users\Start Menu\Programs\Startup and paste the Outlook shortcut.
Close Windows Explorer and Outlook should now startup when your computer does.