Since you don't have any links pointing from the homepage to other pages. The only information you have is the URL of the homepage and the URL pattern used for accessing the users.
The only possibility I see it then to use a dictionary of names, or all possible string permutations with a limited length. And then accessing every single one of them.
Have a look at http://docs.python.org/2/library/urllib.html in order to see how you can create HTTP requests/open URLs.
Then write a loop that iterates through all names/string permutations and calls the URL.
You might consider doing this concurrently, which should be relatively easy to achieve: http://en.wikipedia.org/wiki/Embarrassingly_parallel