AFAIK, the email address should support non-ASCII character (from https://stackoverflow.com/questions/760150/can-an-email-address-contain-international-non-english-characters and SMTPUTF8 
 option from https://docs.python.org/3/library/smtplib.html#smtplib.SMTP.sendmail)

>>> import smtplib
>>> s = smtplib.SMTP(host='smtp-mail.outlook.com', port=587)
>>> s.verify('你好@outlook.com')
Traceback (most recent call last):
  File "<stdin>", line 1, in <module>
  File "/Users/windson/learn/cpython/Lib/smtplib.py", line 577, in verify
    self.putcmd("vrfy", _addr_only(address))
  File "/Users/windson/learn/cpython/Lib/smtplib.py", line 367, in putcmd
    self.send(str)
  File "/Users/windson/learn/cpython/Lib/smtplib.py", line 352, in send
    s = s.encode(self.command_encoding)
UnicodeEncodeError: 'ascii' codec can't encode characters in position 5-6: ordinal not in range(128)

I found this issue when I updating https://github.com/python/cpython/pull/8938/files