Yes, you can send emails on behalf of the 'Record Owner', or 'Logged-In User', or 'Global Sender' (set in MassMailer Settings), or 'Organization-Wide-Address' that you have set in Salesforce.

You can also set any email id as From / Reply-To address but please note that it is a best practice to use the same domain email id as the sender otherwise your email may get flagged as spam.