Answer: Web services can only be invoked by HTTP (traditional webservice with .asmx). While WCF Service or a WCF component can be invoked by any protocol (like http, tcp etc.) and any transport type.
Second web services are not flexible. However, WCF Services are flexible. If you make a new version of the service then you need to just expose a new end. Therefore, services are agile and which is a very practical approach looking at the current business trends.
We develop WCF as contracts, interface, operations, and data contracts. As the developer we are more focused on the business logic services and need not worry about channel stack. WCF is a unified programming API for any kind of services so we create the service and use configuration information to set up the communication mechanism like HTTP/TCP/MSMQ etc
For more details, read
http://msdn.microsoft.com/en-us/library/aa738737.aspx