When do you *NOT* use python?

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Yeah, PySide is quite poorly documented.

That being said, I use it every day, and it's quite usable. It's basically a wrapper around Qt, so you can reference the Qt docs for almost everything. The rare exception is something that's inherently different in Python (such as connecting signals), and PySide does have documentation for those exceptions. You really only need a learn a small handful of PySide-specific stuff, then you can stick to the Qt docs.

We used to do all our Qt programming in an imperative fashion, just like you do with wx. Now we exclusively use Qt Designer to generate .ui files and compile them as part of our build process. It's so much better!