diff --git a/requests/models.py b/requests/models.py
index 072336b2..c70b56f5 100644
--- a/requests/models.py
+++ b/requests/models.py
@@ -9,6 +9,7 @@ This module contains the primary objects that power Requests.
 
 import collections
 import datetime
+import codecs
 
 from io import BytesIO, UnsupportedOperation
 from .hooks import default_hooks
@@ -580,7 +581,8 @@ class Response(object):
         #: Final URL location of Response.
         self.url = None
 
-        #: Encoding to decode with when accessing r.text.
+        #: Encoding to decode with when accessing r.text or 
+        #: r.iter_content(decode_unicode=True)
         self.encoding = None
 
         #: A list of :class:`Response <Response>` objects from
@@ -670,8 +672,8 @@ class Response(object):
         chunks are received. If stream=False, data is returned as
         a single chunk.
 
-        If decode_unicode is True, content will be decoded using the best
-        available encoding based on the response.
+        If using decode_unicode, the encoding must be set to a valid encoding 
+        enumeration before invoking iter_content.
         """
 
         def generate():
@@ -708,6 +710,16 @@ class Response(object):
         chunks = reused_chunks if self._content_consumed else stream_chunks
 
         if decode_unicode:
+            if self.encoding is None:
+                raise TypeError(
+                    'encoding must be set before consuming streaming '
+                    'responses'
+                )
+            
+            # check encoding value here, don't wait for the generator to be
+            # consumed before raising an exception
+            codecs.lookup(self.encoding)
+            
             chunks = stream_decode_response_unicode(chunks, self)
 
         return chunks
diff --git a/requests/utils.py b/requests/utils.py
index 6a3ed90e..7d7a516b 100644
--- a/requests/utils.py
+++ b/requests/utils.py
@@ -368,11 +368,6 @@ def get_encoding_from_headers(headers):
 def stream_decode_response_unicode(iterator, r):
     """Stream decodes a iterator."""
 
-    if r.encoding is None:
-        for item in iterator:
-            yield item
-        return
-
     decoder = codecs.getincrementaldecoder(r.encoding)(errors='replace')
     for chunk in iterator:
         rv = decoder.decode(chunk)
diff --git a/tests/test_requests.py b/tests/test_requests.py
index d8d7ea54..cc621a20 100755
--- a/tests/test_requests.py
+++ b/tests/test_requests.py
@@ -1039,9 +1039,24 @@ class TestRequests:
         r = requests.Response()
         r.raw = io.BytesIO(b'the content')
         r.encoding = 'ascii'
+
         chunks = r.iter_content(decode_unicode=True)
         assert all(isinstance(chunk, str) for chunk in chunks)
 
+    @pytest.mark.parametrize(
+        'encoding, exception', (
+            (None, TypeError),
+            ('invalid encoding', LookupError),
+        ))
+    def test_decode_unicode_encoding(self, encoding, exception):
+        # raise an exception if encoding isn't set
+        r = requests.Response()
+        r.raw = io.BytesIO(b'the content')
+        r.encoding = encoding
+
+        with pytest.raises(exception):
+            chunks = r.iter_content(decode_unicode=True)
+
     def test_response_reason_unicode(self):
         # check for unicode HTTP status
         r = requests.Response()