This book is awesome. It may take quite a while to internalize all the useful stuff that it says about PostgreSQL. Just the chapter about Query Optimization is worth buying it for.
The author is an experienced PostgreSQL administrator and he shares quite a lot of experience. If you're a programmer, it will help you understand a lot of things about PostgreSQL performance that you have never considered before – hard disk configuration and performance, the importance of the Write-Ahead Log and checkpoints, how MVCC is implemented and why some things are slower than expected (for example, `SELECT COUNT(*) FROM tablename` usually needs to do a full-table scan instead of just returning a number immediately).
I won't go into everything I've learned from the book, since it will take quite a while to read it. I'll just mention that you should definitely read it if you're serious about your work with PostgreSQL.