The thing with python standard library is that it is crapily documented imho. I often can't make heads or tails of it, while I have a much simpler time with any other language (you name it: Java, Ruby, PHP, C, Scala, Lisp, ...).
I also highly recommend checking out Doug Hellman's book 'The Python Standard Library by Example'. He presents every (or almost every) standard library module with simple explanations and plenty of examples.
Except for some of the "batteries included" stuff. urllib2? Ouch.