Requests is great by the way, had already written some code to abstract away the urllib/urllib2 mess but this module is so much more complete (of course) and cleaner.
A good example is C#/.NET issues (and somewhat java) where you have .length .Length and .Length() and .Size() and .Count() and so on. It makes changing a data type an exercise in annoyance, and on the one hand there is a decent argument about semantic meaning of the name, on the other hand, tracking each and every subtle use of "I need to know how many things I'm dealing with" in several different ways becomes an exercise in yak shaving.
As for the specific of .json - A lot of python web frameworks provide a .json attribute/property to the request structure, so I presume the earlier version of Requests was mirroring that for conceptual continuity.
I'm not sure why java uses .length for arrays and .size() for collections ... but could it be that it was for similar reasons?