Think of the List interface as a guarantee. Any class that implements List will be guaranteed to have the methods of the interface. When Arrays.asList() returns a List you're not actually getting an interface, you're getting a concrete class that is guaranteed to implement the methods listed in the List interface.
As to your "we should never really use a interface type variable" you're actually suppose to do that. It's called "programming to the interface". It's much more flexible if you can return a List as opposed to something like a LinkedList. The caller of your method isn't coupled to your specific implementation internal implementation which might use, and return, a LinkedList. If at some point you wanted to return a ArrayList instead of the LinkedList the caller would not have to change any code because they only care about the interface.
What does it mean to "program to an interface"?
Just a word of note, Serializable is a marker interface and a little odd because of that. It doesn't guarantee that methods are there, but instead guarantees that the creator of the class that implements serializable has thought about the many issues associated with serializing a class (overriding readObject/writeObject, compatiblity with other serialized forms, and other issues http://www.javapractices.com/topic/TopicAction.do?Id=45). So Serializable is still offering a guarantee, like List is, but it isn't about method signatures, it's about an extralinguistic feature of the language.
http://en.wikipedia.org/wiki/Marker_interface_pattern