I know some Python and I'm really impressed by the language's ease of use. From what I've seen of Objective-C it looks a lot less pretty, but it seems to be the lingua franca for Mac OS X development (which means it has better documentation). 
I'm thinking about starting Mac development - will using PyObjC+Python make me a second class citizen?
You're going to need Objective-C: that's what all the tutorials, documentation, sample code, and everything is written in. In addition to a wilder variety of people being able to help you.
So learn ObjC first. If, on your second or third project, or a year down the road, you start a project that needs a Python module (like, say, Twisted, or SQLAlchemy. But a SERIOUS need like foundation of your app need, where the extra boost your app gets makes everything worth it), then you can write a PyObjC app and get a lot of the speed benefits of that language, with your background in Cocoa.
What are the downsides of using Python instead of Objective-C?