After returning from Facebook headquarters to hear Mark Zuckerberg make his "awesome" announcement, I had a chance to try out the new Facebook video chat which is powered by Skype. The service lets you establish a call with anyone who is currently a Facebook friend. You can't chat with non-friends and you can't chat with Skype users who aren't using Facebook. Also new is a "buddy list" window on the right side of the monitor, assuming your monitor is big enough. You might not see it if you're using a notebook PC.
Starting the process
The process begins with setting up a text chat with someone which you can now do by clicking on that person's name in the sidebar (assuming you have a large enough monitor). Once you're in the chat window, click on the video camera in the top blue bar.
You will see a message telling you that you're waiting for the person to answer.
The person who you calling will see a message asking them to accept that call.
When you're done, click the X in the upper right corner to close the window and end the call.