I got this error from Application Loader when uploading my app to App Store. My app was developed at the time of iOS 3.0, and still targets at iOS 4.3 and above. I recently updated the app to make it iOS7-compatible. But the Application Loader always returned this type of error to me. I searched the Internet and found that I am not alone. So I created this post and hopefully what I found out about the app icons can help other people.
Sounds like you may, like me, have accepted the suggestion by XCode 5.0 to migrate your icon files to a catalog.
When you do that, you need to remove the CFBundleIconFile ("Icon file") parameter from your project's .plist file. That's the old way of doing this, and once you've migrated your icon files, obviously that parameter is incorrect.
Strange that XCode's migration doesn't fix this for you automatically. Would have been so very Apple to help you out there.