Я делаю это так:
def send_mail
msg['Subject'] = subject
msg['From'] = sender
msg['To'] = [email1@to.de,email2@to.de]
msg['Cc'] = [email3@cc.de,email4@cc.de]
msg['Bcc'] = [email5@bcc.de,email6@bcc.de]
recips = [email1@to.de,email2@to.de,email3@cc.de,email4@cc.de,email5@bcc.de,email6@bcc.de]
sendmail(sender, recips, msg.as_string())
msg['From'] = sender
msg['To'] = [email1@to.de,email2@to.de]
msg['Cc'] = [email3@cc.de,email4@cc.de]
msg['Bcc'] = [email5@bcc.de,email6@bcc.de]
recips = [email1@to.de,email2@to.de,email3@cc.de,email4@cc.de,email5@bcc.de,email6@bcc.de]
sendmail(sender, recips, msg.as_string())