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if I have the following web app domain username.pythonanywhere.com, does that mean I also have the following email username@pythonanywhere.com?

using send grid, I seem to be able to send emails from username@pythonanywhere.com

No. You don't have access to the email username@pythonanywhere.com. You can "send" emails from any email addresses (eg: u could also "send" from stevejobs@apple.com) but you won't be able to receive it.