import tempfile
import win32api
import win32print

filename = tempfile.mktemp (".txt")
open (filename, "w").write ("This is a test")
win32api.ShellExecute (
  0,
  "print",
  filename,
  #
  # If this is None, the default printer will
  # be used anyway.
  #
  '/d:"%s"' % win32print.GetDefaultPrinter (),
  ".",
  0
)

参考 https://timgolden.me.uk/python/win32_how_do_i/print.html