Extensibility is very important feature of any framework and WCF has a lot of extensibility points, Carlos Figueira has posted a full series of blog post on MSDN, Below are the consolidated links from his blog post http://blogs.msdn.com/b/carlosfigueira/archive/2011/03/14/wcf-extensibility.aspx
1. Service model extensibility
1.1. Behaviors
1.1.1. IServiceBehavior
1.1.2. IContractBehavior
1.1.3. IEndpointBehavior
1.1.4. IOperationBehavior
1.2. WCF Runtime
1.2.1. Message interception
1.2.1.1. I[Client/Dispatch]MessageInspector
1.2.1.2. IParameterInspector
1.2.2. Mapping between message and operation parameter
1.2.2.1. I[Client/Dispatch]MessageFormatter
1.2.3. Mapping between message and CLR operations
1.2.3.1. I[Client/Dispatch]OperationSelector
1.2.3.2. IOperationInvoker
1.2.4. Instance [context] creation / initialization
1.2.4.1. IInstanceProvider
1.2.4.2. IInstanceContextProvider
1.2.5. Error handling
1.2.5.1. IErrorHandler
1.2.6. Others
1.2.6.1. Initializer interfaces (IInstanceContextInitializer / IChannelInitializer / ICallContextInitializer)
1.2.6.2. IInteractiveChannelInitializer
1.3. Exposing / consuming metadata
1.3.1. IWsdlExportExtension
1.3.3. IPolicy[Import/Export]Extension
1.4. Configuration
1.4.1. BehaviorExtensionElement
1.4.2. BindingElementExtensionElement / StandardBindingElement / StandardBindingCollectionElement
1.5. Web Hosting
1.5.1. ServiceHostFactory
1.6. WCF REST (3.5 / 4.0 model)
1.6.1. QueryStringConverter
1.6.2. Extending WebHttpBehavior
1.7. Others
1.7.1. Extensible objects: IExtensibleObject<T> and IExtension<T>
2. Channel extensibility
2.1. Protocol channels (client)
2.2. Protocol channels (server)
2.3. Message encoders
2.4. Transport channels
2.4.1. Request transport channels - part 1 (synchronous path)
2.4.2. Request transport channels - part 2 (interaction with runtime extensions)
2.4.3. Request transport channels - part 3 (asynchronous path)
2.4.4. Reply transport channels
2.4.5. Duplex transport channels
3. Serialization extensibility
3.1. Serialization callbacks (On[Ser/Deser]ializ[ing/ed])
3.3. DataContractResolver
3.4. IExtensibleDataObject / IDeserializationCallback / IObjectReference
4. Miscellaneous extensibility scenarios
4.1. Hooking into the tracing mechanism
4.2. Custom serialization in Silverlight 4
4.3. Extensibility in Windows Phone / Silverlight 3
4.4. WCF RIA Services