Related Questions:
How do I share a Document with someone who isn't in Event Temple?
Send a contract to someone that is not the primary contact
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Answer:
To send an email directly to someone using the "To:" recipient field they must be a Contact within Event Temple.
You can CC or BCC an email address that is NOT a Contact in Event Temple. This is not recommended since the person does not have a Contact profile for you to refer to.
After typing the email address, click "new" to add them as a Contact or the Enter key to properly enter the email address.