Pylons is awesome because its purpose is to provide me with the magic that makes Python websites easier and that's it. After that, it leaves me alone to write Python. It doesn't impose a certain toolkit on me; though Pylons suggests a certain ORM and templating language, there is no obligation to use them, and everything will swim along just swimmingly if I want to use something else. These things are all replaceable and interchangeable.
In my mind, Pylons is what a framework should be. It gives you a handy set of conveniences, functions, and configurations designed to overcome and share much of the monotonous and repetitive solutions necessary to reach the specified end (in Pylons's case, developing web apps in Python) and then it gets out of your way.
When I write Pylons, I am mostly writing Python; it's just like any other Python application, except in the places where I want a shortcut specific to the web-based nature of my program, and then it's an elegant, unassuming function name or shortcut that doesn't get in the way or announce itself.
However, when I've used other frameworks, like Rails and CakePHP, I've felt more like I am writing programs in Rails or CakePHP than "real" Ruby or "real" PHP. They all seem to demand a way of doing things that's quite different from the usual flow of those languages, and the resulting apps don't feel like apps anyone who reads Ruby or PHP could follow. CakePHP particularly has its own implementation of almost everything and relatively few lines of pure PHP ended up in the codebase.
Worse, those frameworks were tightly coupled with their custom ORMs, templating languages, and other important affixes that really deserve their own projects. Pylons's assumed toolkits are full-fledged, external projects, and if I don't like their suggestions of Mako and SQLA, it's really easy to drop in whatever suits my fancy. It's done in the normal Python way. Pylons isn't going to give me any extra guff over it, and it doesn't care if I use SQLAlchemy or DB-API directly or whatever I want to use.
I really love Pylons for all of this. I hope more frameworks start adopting these philosophies.