I had the same error message, despite adding Calibre to firewall connections. Turns out my virus checker (McAfee) was refusing to send the email (as part of the protection against worms sending out mass mailings). If you check your virus checker, it will probably save a log somewhere - for McAfee it was in C:\Documents and Settings\All Users\Application Data\McAfee\DesktopProtection\AccessProtectionLog. txt. Doing a search for 'calibre' in this found the message:
"10:49:54 AM Blocked by port blocking rule C:\Program Files\Calibre2\calibre.exe Anti-virus Standard Protection:Prevent mass mailing worms from sending mail 74.125.53.109:587".
There will be an options or preferences settings in your software that lets you specify 'calibre.exe' as an exception, allowing it to send emails. After doing this in McAfee, the email is working fine.
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