If you need to change the AlternateEmailAddresses to $null for a user account or tenant admin you cannot, however, it has to be an array as below.
To check if the user has any alternate email address setup, use below command:
Get-MsolUser -UserPrincipalName email[at]contorso.com
To set alternate email address for a user as $null use the below command:
Set-MsolUser -UserPrincipalName email[at]contorso.com -AlternateEmailAddresses @()
The @() will create an empty array.
More details about empty PowerShell arrays here.
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GA IT Support » Office365 » How to remove O365 alternate email address