UPDATE
According to a Tweet from Colin Blair you can also add the RiaServices.EntityFramework NuGet package to your project to fix this issue.
https://twitter.com/ColinBlair/status/328927765871079426
The problem
The problem can be recreated by the following:
- Ensure your have a primary key defined in your table
- Create a new Silverlight Project, enable RIA services
- On the server side add a new Data Model then rebuild the solution
- Click on "Add" -> "New Item" -> "Domain Service class"
- You see a new "Add Domain Service Class" window but the classes from your model do not show up for use.

The Solution
The Solution is:
- Open your Model (.edmx file) in Model Designer (just double-click)
- Right-click in an empty space within the Model Designer & choose "Properties"
- Change the value of "Code generation strategy" from "None" to "Default"

- Select the Server Project Name (for example MyExample.Web) & click on the "Show All files" button on:

- Expand the "model.edmx" file & locate & delete the 2 .tt files.

- Rebuild the solution
- Now click on "Add" -> "New" -> "Domain Service"
Pooff!! This time you will see the classes available in the Add Domain Service Class window.
Hope this helps some poor soul out there like me.

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