How can I extract all mailbox names and email addresses in my entire organization?

Question:
How do I get a list of all mailboxes in my Exchange organization, with their SMTP addresses?

Answer:
The most appropriate report template to use would be Selected Attributes From Mailboxes, that you will find on the Templates > Inventory menu.

You would select all mailboxes in the organization, select at least three attributes (First name, Last name, Email address) and export your report as a CSV file, and then open that file in Excel.
 
 
You would obtain a report such as this one:
 

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