<p>We use a lot of of python to do much of our deployment and would be handy to connect to our TFS server to get information on iteration paths, tickets etc. I can see the webservice but unable to find any documentation. Just wondering if anyone knew of anything?</p>

The web services are not documented by Microsoft as it is not an officially supported route to talk to TFS.  The officially supported route is to use their
.NET API
.
In the case of your sort of application, the course of action I usually recommend is to create your own web service shim that lives on the TFS server (or another server) and uses their API to talk to the server but allows you to present the data in a nice way to your application.
Their object model simplifies the interactions a great deal (depending on what you want to do) and so it actually means less code over-all - but better tested and testable code and also you can work around things such as the NTLM auth used by the TFS web services.
Hope that helps,
Martin.