In ReStructuredText, this gets syntax highlighted
because of the code directive [1][2][3]:

.. code:: python

   import this
   def func(*args, **kwargs):
       pass

This also gets syntax highlighted as python[3]:

.. code:: python

   import this
   def func(*args, **kwargs):
       pass

This does not::

   import this
   def func(*args, **kwargs):
       pass

Syntax highlighting in Docutils 0.9+ is powered by Pygments.
If Pygments is not installed, or there is a syntax error,
syntax highlighting is absent.

GitHub does show Pygments syntax highlighting
in .. code:: blocks for .rst and .restructuredtext documents [4]

1. Does the python.org PEP view support .. code:: blocks? [5]
2. Syntax highlighting is an advantage for writers, editors, and readers.
3. Should PEPs use .. code:: blocks to provide this advantage?

[1] http://docutils.sourceforge.net/docs/ref/rst/directives.html#code
[2] http://www.sphinx-doc.org/en/stable/markup/code.html
[3] http://www.sphinx-doc.org/en/stable/config.html#confval-highlight_language
[4] https://github.com/python/peps/blob/master/pep-0557.rst
[5] https://www.python.org/dev/peps/pep-0557/

https://www.python.org/dev/peps/pep-0458/