When thinking about a new web application I like to try to think about the URLs that my application has. The URLs are the bits that expose my application to the outside world, they define what my application can do, so thinking about them early on means that I'm focusing one of the most important parts of my system.
As I develop complex web systems I've found that creating an organised, consistent URL system has significant benefits to my code-base overall and makes my systems easier to create and maintain. At the same time I notice that beginning developers often create overly complicated and disorganised URL structures for their applications.