The documentary is a melange of historian interviews, narrative voice-over and re-enactment. The re-enactment was a bit jarring because of the long hair on the men (I guess I expected closely cropped hair, I'm not sure why), and the sparse set dressing, but I'm just jaded from watching HBO's Rome too many times. I can't comment on the accuracy because I'm ignorant about the Hittites (that's why I watched the DVD), but I find the bronze age fascinating in general, and it seems in keeping with what I have read from The Cambridge Ancient History Volume 2, Part 2: The Middle East and the Aegean Region, c.1380-1000 BC,
I do admit I might only give it three stars without the melliflous narration of Jeremy Irons, gently pronouncing these jawcracker names. There seems to be some disagreement on how to pronounce the names, and the written form (from the Cambridge Ancient History) lists them as having -ash at the end. Hattushilli is Khattushilash, for example, so it make it confusing.
I quite enjoyed this DVD, and have watched it several times. It has surprising production values compare to many shows on the History Channel, and seems to have been promoted by the Turkish government - if so, good for them. Turkey is a deep well of history.
Bottom line, if you're a veteran watcher of History Channel type documentaries, you'll enjoy this.