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I installed postfix and dovecot on my CentOS system. I'm able to send mail fine with my new email address, and the receiver is fine with replying to the message and/or sending mail to my new email address. But this work fine ONLY after I have sent mail first to the receiver.

I attempted to send an email to the new email account with an address that has never previously received mail from it before. When I do this, I get a Mail Delivery System message saying: No Such User Here.

What seems to be the problem here? How to fix it?

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This problem is related to postfix, and has nothing to do with dovecot.

I think most probably it's a typo in the address field!? If you reply a mail you mail client takes care of the correct To:-field.
If this isn't the case you should take a look into you mail.log (probably located in /var/log). What does postfix say when a mail is bounced? Can you tell us the name of your mail account?

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