To send an email with a PDF attachment the following code should work:

msg = MIMEMultipart()
msg['From'] = from
msg['To'] = to
msg['Subject'] = 'test'
fp = open('/path/to/file.pdf', 'rb')
attach = MIMEApplication(fp.read(), 'pdf')
fp.close()
attach.add_header('Content-Disposition', 'attachment', filename = 'file.pdf')
msg.attach(attach)
server = smtplib.SMTP('smtp.example.com')
server.login('username', 'password')
server.sendmail(from, to, msg.as_string())
server.quit()

But an exception is raised:

TypeError: string payload expected: <class 'bytes'>

To work around the problem the code above can be rewritten as follows:

msg = MIMEMultipart()
msg['From'] = from
msg['To'] = to
msg['Subject'] = 'test'
fp = open('/path/to/file.pdf', 'rb')
attach = MIMENonMultipart('application', 'pdf')
payload = base64.b64encode(fp.read()).decode('ascii')
attach.set_payload(payload)
attach['Content-Transfer-Encoding'] = 'base64'
fp.close()
attach.add_header('Content-Disposition', 'attachment', filename = 'file.pdf')
msg.attach(attach)
server = smtplib.SMTP('smtp.example.com')
server.login('username', 'password')
server.sendmail(from, to, msg.as_string())
server.quit()

This works, but explicit encoding should not be necessary.