When we helped to promote the recently released HTML5 Boilerplate in early August, multiple comments were made, which expressed a desire for a full video overview of the template. Thankfully, Paul Irish, the co-creator, recorded a full video walk-through, exclusively for Nettuts+. In this screencast, he meticulously reviews each page, and then further goes on to explain why and when you would use each snippet in your projects.
The product of years of learning, this video is not to be missed! Even if you have no intention of using this template, you'll still learn an array of helpful techniques.
You also might like Paul's "10 Things I Learned from the jQuery Source" screencast. It's equally educational and funny.