Starting to learn any new framework can be a daunting task, and sometimes finding the right learning resources can be hard. Luckily for Node.js there is a free beginner guide book by Manuel Kiessling. It can be found at http://www.nodebeginner.org/ with all the source code available on its GitHub's page.
For me, the author got this book just right. I find many programming books too long and dull; by the time you've finished it you've already forgotten what you've been reading! This book, on the other hand, is short, clear and straight to the point.
It takes you from knowing nothing about Node.js to writing a simple application stack from scratch. Unlike many other tutorials on Node.js, which get you using frameworks, this book takes you through all the basics of what you need to know. I think this is important for anyone learning any new technology; we need a greater understanding of the basics before we can use any framework that abstracts these away.
I cannot recommend this book highly enough if you're wanting to know more about Node.js. What are you waiting for? Go and read it!