I have developed a few application using Flex and Rails. The easiest way is just to use the as3corelib (http://code.google.com/p/as3corelib/) and use standard JSON objects. You can play around with the AMF serializers, but none of them are production ready (they are written in ruby and not C).
The biggest thing you need to make sure of is if you are creating resources from Flex you need to send the authenticity key from flex. I do this by writing a helper to output it to a view:
<script language="Javascript">
function getAuthKey() { return "<%= form_authenticity_token %>"; }
</script>
Then use ExternalInterface to call it inside Flex.
ExternalInterface.call('getAuthKey')