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Opening the this bug following this discussion - http://mail.python.org/pipermail/docs/2012-March/007829.html
library/re.html
\S
When the LOCALE and UNICODE flags are not specified, matches any non-whitespace character; this is equivalent to the set [^ \t\n\r\f\v] With LOCALE, it will match any character not in this set, and not defined as space in the current locale. If UNICODE is set, this will match anything other than [ \t\n\r\f\v] and characters marked as space in the Unicode character properties database.
This is wrong. With LOCALE set, it should be [^ \t\n\r\f\v] plus any non-space character in that locale.

New changeset 2d2a972b7523 by Senthil Kumaran in branch '2.7':
Fix closes issue14258 - added clarification to \W and \S flags
http://hg.python.org/cpython/rev/2d2a972b7523 

This clarification is specific to Python 2.7. 
For Python3, the use of LOCALE flag is explicitly discouraged and
confusing references to it's meaning is not present in the docs.

Well, I would like to correct this further and add clarification based on the current implementation (_sre.c)
The definition of LOCALE Space is this -
 #define SRE_LOC_IS_SPACE(ch) (!((ch) & ~255) ? isspace((ch)) : 0)
And the definition of NON_SPACE category is a negation of space. That's it.
Now, given that definition, we see for the character values higher than 255, the check is not made at all. Is it simple ascii isspace is considered when the LOCALE flag is set. And in effect, re.LOCALE flag has not extra effect on matching of space or non-white space character.
After realizing this, I propose the following changes attached in the patch as a documentation fix.

New changeset 4d49a2415ced by Senthil Kumaran in branch '2.7':
Fix closes Issue14258 - Clarify the re.LOCALE and re.UNICODE flags for \S class
http://hg.python.org/cpython/rev/4d49a2415ced