Successfully sending e-mail generally requires a queue where a message can sit for seconds, minutes, or days until it can be successfully transmitted toward its destination. So you typically do not want your programs using Python’s smtplib to send mail directly to a message’s destination—because if your first transmission attempt fails, then you will be stuck with the job of writing a full “mail transfer agent” (MTA), as the RFCs call an e-mail server, and give it a full standards-compliant re-try queue. This is not only a big job, but also one that has already been done well several times, and you will be wise to take advantage of one of the existing MTAs (look at postfix, exim, and qmail) before trying to write something of your own.
So only rarely will you be making SMTP connections out into the world from Python. More usually, your system administrator will tell you one of two things: