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I have a @hotmail.com address that was used to connect to my Windows 8 local user account. This is the account that shows up in the Users app, as well as on the lock screen.

I also have an aliased @outlook.com that I would like to use instead as the login name is nicer. Is it possible to change the app to use the alias instead? When I tried to log in during setup with the @outlook.com address it told me to use the master @hotmail.com address instead.

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I'd recommend switching to a local account first:

http://www.eightforums.com/tutorials/4842-local-account-switch-windows-8-a.html

After that has been done sign in with your new hotmail account.

http://www.eightforums.com/tutorials/4840-microsoft-account-switch-windows-8-a.html

I should also note that any purchases made in the old account will not be transferred over (99% about this)

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You have to wait unless Hotmail itself is migrated to Outlook completely. Till that time, the answer to your question is no

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