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After you add your domain to Office 365, you can send and receive email using an email address, like firstname.lastname@example.org, in the Office 365 portal. If you also want to use Office 365 email with your Outlook program on your desktop, you can do that too. (If you have Outlook 2010 or 2007, make sure you’ve run Office 365 desktop setup first so they’ll work correctly.)
Tip You can also set up Outlook to work with your original onmicrosoft.com email address, if you don’t have a custom domain or you’re just trying out the service.
For Office 365 email to work with Outlook, it first has to be set up correctly in the service.
You might want to set up Outlook with two or more email addresses (or accounts). Then you can set an option so that you’re prompted, each time you run Outlook, to choose one.