Web services allow applications to communicate over the web through XML. Windows Communication Foundation (WCF) and Web API both enable building web services, but WCF focuses on interoperability across protocols while Web API is ideal for building RESTful services compatible with browsers and devices. WCF supports features like transactions and reliability but requires defining bindings, while Web API is simpler and uses HTTP verbs for CRUD actions. The choice depends on requirements for interoperability versus a RESTful approach.