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I'm on Windows 8 Pro and have recently begun testing Office 2013 Pro Plus. Unfortunately during the setup of Outlook it will not connect up to my Office 365 e-mail address. I uninstalled Office 2013 Pro Plus and put the previous Office 2010 Pro Plus on and it worked straight away...
Seems like Auto-discovery of Office365 exchange is broken in Outlook 2013?
According to your description, I suggest you use the Remote Connectivity Analyzer to check if there’s anything wrong with your Outlook Autodiscover.
If the Autodiscover works fine, it is recommended that you refer to Set up email in Outlook 2010 or Outlook 2013 to try it again.
Have you resolved this issue? Please let us know if you need further assistance.