First thing to check is to ensure that the Silverlight app is pointing at the production service rather than still at the VS2010 one (ie, localhost:####). There's a few ways to handle this, like generating the WCF service call based on current server your app is coming from, getting the service live on production and updating the service reference to point at the new location, etc.
Another thing to be careful of is that when you move from the VS2010 environment to live you must ensure that your application and service can still access your database. If the user the service is using on IIS doesn't have permission or your connection string hasn't been updated, it sometimes seems like a WCF error (I think it pulls up server error 500 or the fun NotFound) but is actually your service unable to work with the database.
Otherwise, as Marek said more details are always helpful as a lot of things can go wrong in deployment/configuring WCF with Silverlight if you're not careful.