Don't miss this GREAT Book:
Ron Jacobs, (Senior Technical Evangelist for WCF at Microsoft) wrote on its forewords that "The best testament to this is to wander the halls of building 42 in Redmond (where the WCF team works); in many of the offices you will see Programming WCF Services on the shelf."
So from that I gathered that the team at Microsoft first wrote WCF and then they bought this book to understand what they actually have written!!
But seriously, I strongly recommend this book not to only understand WCF but also to learn how Juval Löwy - one of the most prominent distributed systems experts in the world today - thinks and looks at WCF and the concept of designing Enterprise SOA applications in general.