Yes you can do this. You'll need to make use of two features: metadata mapping and relationship connections (if you are using Core Data).
Metadata mapping exposes a bunch of additional information to the mapping engine that is not directly available from the parsed JSON document. The URL itself is part of this as well information from the routing process, HTTP headers, etc.
If you are using Core Data, then you can map the :userID out of your URL and then use an `RKConnectionDescription` to establish a Core Data relationship between a User and his friends by primary key.
There are some great example in the test suite for using metadata mapping to pull info out of URL's like this.