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I have just installed the Office 2016 Preview and am severely disappointed to find that I cannot send from the alias within the new client.
It's a work in progress in conjunction with the move of Outlook.com to the Exchange Online platform. Once that is completed and your account has been migrated, sending from an alias address will be possible without any additional configuration in Outlook 2010 or later.
Until then, you can configure the alias as an additional POP3 account and configure it for sending only.
I can select the alias email address from the From: dropdown menu, but how to I make this the default? I use my personal domain email address and would like this to be my default. It is so simple on Outlook.com, why isn't even more simple in Outlook 2016, a major part of the Office suite! Very frustrating.......