Another way to block skype, please read Block Skype by p2p filter module in Active Wall.
Skype will readily leak out of the network, using high-numbered ports—either TCP or UDP. As a last resort, it will use ports 80 and 443, which are most commonly used for Web traffic.
Step 1. Port Filter Config
The Skype client uses high-numbered ports to connect SkypeNet.
We can block high-numbered ports, but it is recommended that we should close all ports except some common used ports.