There's quite a bit of new stuff, including some new character art for each character's pages (at least art I haven't seen before). The V cast only gets their usual character art you've seen a million times. It's a decent art book that I'm happy to have in my collection.
The DVD is kind of underwhelming. It features the opening videos from 1-5 as well as some of the more important cutscenes from early in the games. The big downside is the video quality. It just looked bad compared to how they look in the games (save for 1&2, which naturally look better than their Saturn counterparts). At least the DVD is region free. There's also an interview with Kohei Tanaka on there.