The italki website does not have a videocall system.
Italki is mostly a marketplace to connect students and paid teachers. Students and teachers are expected to make their own arrangements for videocalls. Skype seems to be by far the most popular. In your profile, you indicate which kinds of call you can make, from a list that includes Skype, FaceTime, Google Hangouts, QQ, and Wechat. The teacher does the same. When you make an appointment you say which kind you will use.
It is also a social site for meeting people who want to have language exchanges. All arrangements are completely up to you and your partner. You can make Skype videocalls if your partner agrees to give you their Skype address.