The documentation sources are written in DocBook, which is a markup language superficially similar to HTML. Both of these languages are applications of the Standard Generalized Markup Language, SGML, which is essentially a language for describing other languages. In what follows, the terms DocBook and SGML are both used, but technically they are not interchangeable.
The PostgreSQL documentation is currently being transitioned from DocBook SGML and DSSSL style sheets to DocBook XML and XSLT style sheets. Be careful to look at the instructions relating to the PostgreSQL version you are dealing with, as the procedures and required tools will change.
DocBook allows an author to specify the structure and content of a technical document without worrying about presentation details. A document style defines how that content is rendered into one of several final forms. DocBook is maintained by the OASIS group. The official DocBook site has good introductory and reference documentation and a complete O'Reilly book for your online reading pleasure. The NewbieDoc Docbook Guide is very helpful for beginners. The FreeBSD Documentation Project also uses DocBook and has some good information, including a number of style guidelines that might be worth considering.