Yes, it is possible to have 2 email addresses for an account, provided that your administrator has not claimed the domain (e.g. @docusign.com ) and locked down the system.  The locking down is usually done by administrators for large corporate accounts with an Enterprise Pro plan and who have deployed Org Admin.

Again, dependent on your plan and your business, you can create a separate account for a different organization if you want to keep the electronic paperwork separate for subsidiaries / different business units

I’m trying to do the same thing as the OP, but in my case the second email address is not being accepted.  I have tried adding a different address and that works.  For example, my account is currently under “abc@def.com” but I’m selling the domain, so I need to change it to “ghi@jkl.com” and DocuSign (both iPad app and web site) are failing to change the address (I get a generic error message about “an unknown error” with the email address that I want to use... I can add the address as an additional notification target, but that’s not useful to me).  If I change the profile email to “mno@pqr.com”, then DocuSign accepts it.

I’m on a free account so I use DocuSign just for clients who send me contracts to sign.

Any help would be greatly appreciated as I’ve notified clients about the domain sale and they’re wanting to send new contracts, but I’m not able to configure DocuSign with the correct address!