I've also read the companion PostgreSQL 9 Admin Cookbook. The Admin cookbook is an easier read, but this book had a lot more information I was unaware of and probably hit my weaker knowledge spots. There is very little overlap between the two books.
What surprised me most about this book was how much of it is not specific to PostgreSQL, but in fact hardware considerations and testing that are pertinent to most relational databases. In that sense I wouldn't limit my recommendation to just PostgreSQL, but also to anyone using a relational database on Unix/Linux for a high load project.
The PostgreSQL 9 High Performance book isn't going to teach you too much about writing better queries,day to day management (which is more of the focus of the Admin Book), or how to load data etc, but it will tell you how to determine when your database is under stress or your hardware is failing and adversely affecting your queries and what is causing that stress. It will also provide rules of thumb as to how to pick the best hardware for your project and budget, how to partition your data, what disks to put what kind of data. Various tuning and benchmarking techniques for highload testing.