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If you want to debug your .net EA Addin in a 64bit environment you have to create a small file called ea.exe.config in the directory where ea.exe is placed and the content should be:

<configuration>
   <startup useLegacyV2RuntimeActivationPolicy="true">
     <supportedRuntime version="v2.0.50727"/>
     <supportedRuntime version="v4.0"/>
   </startup>
</configuration>