In simplest terms, WCF can do everything Web Services can do and WCF can do even more. Web services are easy to develop, but the only do a limited set of data transports and methods. WCF has a wide range of web standard and .NET-specific transports that can be used in combination. Here is an article that will help you out:
What's the Difference between WCF and Web Services?[
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Even though Web Services are easier to do, unless you are comfortable locking yourself into one way of doing things, go with WCF. You can still do what the Web Services would have done for you but now you can be more flexible for the future. For example, I recently created a WCF service at work. Right now, all of our clients are using HTTPS to connect to it for testing. However, once we deploy it live, we will use Named Pipes since it is much faster (WCF and the front-end will be on the same server). However, down the road I am planning for us to provide access to the WCF service to mobile clients directly. This would mean adding HTTPS access. To do so, it will simply require us to add info to the config file. A five-minute change will allow us to provide different access to different clients.