Microsoft 365 features that help users manage their subscriptions, account settings, and billing information.
Hello AndrewSF-A,
First, I'd like to share with you that to change the primary address synced from local AD to Microsoft 365, please make sure
1, the domain (domain.org) has been added and verified in Microsoft 365 as an accepted domain.
2, the primary email address ******@domain.org not belongs to any other existing users/groups in Microsoft 365 as their SMTP or smtp, otherwise you may get sync error or another temp SMTP for the targeted user in Microsoft 365.
- Please make sure you have set up the correct SMTP/smtp formats for your local AD user like this
Also, please double check if you could find "mail" attribute for the local AD user, if so, please also populate it with the SMTP you set up, and remove the lower-case smtp address for the user then force a DirSync via Start-ADSyncSyncCycle -PoliceType Delta in AD PowerShell module, then wait for some minutes to see if it make any difference, thanks.
Please feel free to let me know if you got any further updates, thanks.
Best Regards,
Oliver