This is without a doubt the best written technical book I've ever read; it's honestly hard to believe only one person wrote and organized it. In an era where you can often get a better answer from a highly voted Stack Overflow question than you'll find most books, TLPI is 100% an exception.
The material is presented in such a fashion that pretty much anyone with a working knowledge of C can pick it up, sit down, and understand any of its topics. Kerrisk often opens with a code-light "overview" chapter on the more dense topics (e.g. networking), and his descriptions are as elegant and well-written as anything you'll find on SO or by googling. He then walks through the topic with an in-depth discussion of the various APIs and excellent example code, crucially often also mentioning now-outdated approaches you will still see pop up, so the reader isn't clueless when encountering pre-POSIX code in real life.
It's the rare book indeed which can serve as both an excellently written (and illustrated!) introduction and reference. If you're a student looking to get into linux systems programming (or been assigned some less than high quality reading), pick this up. if you're a programmer of the type who often finds himself typing "man 2 somethingsomething...", absolutely 100% pick this up. The fact that the author is also in charge of the man pages project for linux shows in his encyclopedic knowledge--what makes this book so outstanding is his ability to present that knowledge in an easily-digested form with tight, well-written examples.
Yes, it's massive. But trust me, there isn't a page wasted in here--even if you're experienced in the area, walking through each chapter and digesting Kerrisk's explanations will serve you well. And to any professors or teachers out there who are curious: yes, please use this as your textbook. As a grad student who hasn't been in CS for very long, I was extremely fortunate to be assigned this as a textbook for a systems programming class. Without this book, there's no way I couldn't have learned as much as I did in a fairly short period of time; more importantly, it made me come to appreciate and enjoy systems programming. It combines the readability/working examples of the best Stack Overflow answers, the comprehensiveness of man pages, and logical progression for new learners in one amazingly tight (if not light) package.