To block skype you need to block at access to the authentication servers. Every Client has to contact to verify the membership and username which is: Skype Auth-Server 80.160.91.11
Skype uses dynamic tcp and udp ports and nat traversal technologies so it makes it difficult to block.
There are a few issues with skype.
1. There code is very heavily guarded and no one really knows what it is doing. I heard of a company in china that was able to crack it.
2. the user agreement states that skype can use your computer as a host and utilize your bandwidth.
Thanks,
Chad
Please rate if this helps!