Rob Hawkes discusses WebRTC, a free, open-source technology enabling peer-to-peer communication in browsers through simple JavaScript APIs, which is similar to Skype but offers more functionality. Key use cases include video/audio calls, screen sharing, collaborative activities, multiplayer gaming, and peer-to-peer file sharing. Despite being a relatively new technology with ongoing developments in browser support, WebRTC facilitates direct connections between users, significantly reducing latency compared to traditional methods like WebSockets.