As nice an idea as that is, unfortunately there are just too many sites to block. If you block the sites that he goes to frequently and he truely has an addiction problem, he will most likely just end up going to another poker site. I don't believe that this is an issue that you can resolve with tech.
Keeping all that in mind, it is possible to prevent sites from loading up properly based upon their domain name. Check out information about creating a
Hosts file.