By default Visual Studio 2010 comes with .Net 4 Framework Client Profile (for desktop applications). The System.ServiceModel.Web.dll is not available in this case.
The targeted framework should be changed to .Net 4 Full.
Here are the steps:
1. Right click on the project where you want to add the System.ServiceModel.Web reference.
2. Go to the Application tab.
3. Choose .Net Framework 4.
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