Hi N,
Based on my knowledge, many methods work with Autodiscover for multiple SMTP domains at on-premise Exchange 2010 server, such as HTTP redirect. Moreover, different methods have different requirements, such as certificate requirement.
In addition, SRV method for Autodiscover is not supported at Hybrid deployment currently.
For detailed information about deploying on-premise Exchange 2010 server, I suggest post the detailed information, such as current on-premise environment and detailed requirement, at the following on-premise Exchange 2010 TechNet forum. This is so you will get better assistance on the deployment.
http://social.technet.microsoft.com/Forums/en-US/exchange2010/threads
As for SMTP domains used at hybrid deployment, please provide more detailed information.
1. Do the users need to be moved to Office 365 have same suffix, such as domain.com?
2. Are the other SMTP domains used for on-premise mailboxes’ primary SMTP addresses?
3. Please provide a detailed example of the requirement.
Thanks,
Claud