The class io.StringIO works with str objects in Python 3. That is, you can only read and write strings from a StringIO instance. There is no encoding -- you have to choose one if you want to encode the strings you got from StringIO in a bytes object, but strings themselves don't have an encoding.
(Of course strings need to be internally represented in some encoding. Depending on your interpreter, that encoding is either UCS-2 or UCS-4, but you don't see this implementation detail when working with Python.)