Django vs. Pylons
I'm using Pylons right now. The flexibility is great. It's all about best-of-breed rather than The Django Way. It's more oriented toward custom application development, as opposed to content-based web sites. You can certainly do content sites in it; it's just not specifically designed for them.
On the other hand, you do end up needing to read a lot of different documentation, in different places, of different quality, to grok all the components. Whereas one of the nice things about Django is that for all the core components, you just read "the" documentation.
The Mako (templates) + SQLAlchemy (DB & ORM) combo is really nice, though. Back when I used Django, I replaced its templating and DB system with them (giving up some of its integration features in the process) and they are standard with Pylons. Mako lets you use Python expressions, which is nice because even though you should separate business logic from design, dynamic sites do require significant display logic, and Django's template tags are clumsy to work with. SQLAlchemy lets you work with the same data model anywhere from the raw SQL level to the object-oriented ORM level.
I think it's worth the time to at least go through the docs and do the QuickWiki tutorial.
Pylons is not that much simpler than Django and it doesn't seem to have the same community. For lightweight apps I would recommend web.py. Even though there is a little magic, it doesn't feel like it. You see everything you do. For lots of other ideas see this very current list of web resources on python.