It's possible to use Web.config Transformations for App.config files through a workaround.
You simply have to invoke the appropriate MSBuild tasks at the right stage in your build process.
Add this code snippet to your project file:
<UsingTask
TaskName="TransformXml"
AssemblyFile="$(MSBuildExtensionsPath32)\Microsoft\VisualStudio\v10.0\Web\Microsoft.Web.Publishing.Tasks.dll" />
<Target Name="AfterCompile" Condition="exists('App.$(Configuration).config')">
<!-- Generates the transformed App.config in the intermediate directory -->
<TransformXml
Source="App.config"
Destination="$(IntermediateOutputPath)$(TargetFileName).config"
Transform="App.$(Configuration).config" />
<!-- Forces the build process to use the transformed configuration file -->
<ItemGroup>
<AppConfigWithTargetPath Remove="App.config"/>
<AppConfigWithTargetPath
Include="$(IntermediateOutputPath)$(TargetFileName).config">
<TargetPath>$(TargetFileName).config</TargetPath>
</AppConfigWithTargetPath>
</ItemGroup>
</Target>
Then add additional App.config files to your project for each build configuration where you wish to apply a transformation. For example:
<ItemGroup>
<None Include="App.config" />
<None Include="App.Release.config">
<DependentUpon>App.config</DependentUpon>
</None>
</ItemGroup>
Related resources: