Up front: I'm a big Realms fan, so take this with a grain of salt.
Disclosure out of the way, I think this book is a solid Realms resource, that is equally useful to players and DMs.
It's the first book I've seen that really uses substitution levels properly. That is, several of the monk, druid and paladin organizations the substitution levels are designed for are themselves fully fleshed out later in the book, and properly (read: thematically) fit Realmslore while remaining reasonably balanced. These organizations are termed ‘Valorous Organizations.’
Something else I like about this tome is that it introduces new Realmslore. I like how the designers saw fit to give enough fluff and crunch to run whole campaigns around (such as a campaign set in Impiltur, where the players build valorous characters that are members of the Knights of Imphras II, and do such things as questing for the lost blades of Imbrar and putting down various fiends and worse from the era of ancient Narfell).
Additionally, CoV lists 66 minor valorous organizations that characters could be a part of or be made to interact with by DMs. It also has a fairly creative list of 50 things for valorous characters to do.
When new Realms sourcebooks come out, I don't always have the time to read them word for word. This is the first book since Lost Empires of Faerûn that I've wanted to read cover to cover (I'm on page 81; 157 pages in the book).
J. Grenemyer