First, the videos are flv files, so you can only play them on your PC, not on your DVD player. You can copy the files to your PC and view them with any flv player. Which you may want to do, since the player that comes on the DVD doesn't seem to allow you to skip around when viewing a video. An annoying oversight.
What about the content? It's OK as an overview of some basic things to consider when creating a site, such as how titles impact search engines or keeping accessibility in mind. However, there's not much detail on each topic; she keeps referring you to her book. You will sometimes get new terms thrown at you without explanation.
So it's more of a springboard to direct you to investigate these topics on your own. As such, I would recommend getting a good book instead, and many are available at this price point that will actually make you an expert. You're not going to get enough detailed knowledge here to "master" anything.
It's nice to see how layouts change in response to CSS changes, but sometimes they ill-advisedly cut to video of her talking instead of staying on the DreamWeaver view.