Anyone can read a reference manual, but the reference often neglects the fundamental principals. I remember when I first started trying to learn Windows in 1991. I always ended up having more questions than answers at the end of the day (thank God for Charles Petzold!). My inexperience was partly to blame, but I have never forgotten those days, and I hope that beginners who read my book will learn from the lessons that I've managed to learn only with great pain. However, I also wrote this book for professional VB gunslingers who have been using the language for years to bring home the bacon. In some ways, VB.NET is a familiar friend. In others, it's an entirely new beast.
If you are looking for a language reference, this ain't it. If you are new to programming, though, you will need a reference. I suggest O'Reilly's VB.NET Language in a Nutshell by Steven Roman, Ron Petrusha, and Paul Lomax, which is concise and user friendly.
If you are not new to programming, a week and a help file is all you need to learn the language's syntax (OK, I am exaggerating a bit). Although this book is not a language reference, you can learn a lot from the example code; much of the VB.NET syntax is used within context.