Web services allow communication between electronic devices over the internet. They use standard protocols like HTTP and XML formats. In J2EE, there are two main types of web services - big web services that use SOAP and WSDL specifications to define operations via XML messages, and RESTful web services that are better integrated with HTTP and do not require XML or WSDL. Web services in J2EE provide benefits like integrating applications and data across different platforms, reusing code, and reducing costs.