Facebook is introduced a new features on its chat windows i.e. facebook video calling.
To make video calls on Facebook you need webcam-equipped computer and then select a friend you want to video chat with. In the chat window that pops up, clicking on a small blue video icon brings up the video chat feature and the first time you will be prompted to download and run a 482KB .exe file. Once the setup downloads and installs the necessary files, you are ready for a face-to-face chat. Currently there is no option to video chat more than one person. That feature is available on Google Plus.
May be you faces an issue "The software that powers video calling is temporarily unavailable. Please try again later."
Some other issues with Facebook video calling are quality of the video, that you have pointed out is better on Skype.