Here’s a quick script for Powershell that can be used to add a secondary SMTP address in Microsoft Exchange 2007.

$username=Read-Host "Enter username to add email address too."
$secondsmtp=Read-Host "Enter a secondary email address"

$usermbx = Get-Mailbox $username
$usermbx.emailAddresses+=$secondsmtp
Set-Mailbox $usermbx -emailAddresses $usermbx.emailAddresses

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