These steps are the same whether you're adding your first email account or additional email accounts to Outlook.
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Select File > Add Account.
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What you see next depends on your version of Outlook.
For Outlook for Microsoft 365 and Outlook 2016, 2019, or 2021
Enter your email address and click Connect.
Enter password, accept the MFA and click Next.
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If prompted, enter your password again, then select OK > Finish to start using your email account in Outlook.