The new feature is free and is available starting Thursday in a "beta" test version of Skype's Mac and PC software.
It expands on an existing partnership between the companies.
Since July, Facebook has allowed users with webcam-equipped computers to make Skype-powered video calls on its site. And it had already been possible to chat with your Facebook friends through Skype's instant-messaging feature, though there wasn't yet a video component.
Skype lets users make calls, conduct video chats and send instant messages over the Web. Its basic services are free, while users pay for services such as calling regular phones from a computer.