Well, to clarify, a lot of popular pre-packaged software is out there in PHP. And PHP never had a good db abstraction layer + the entire style of the PHP language lent itself to the direct use of queries in the code, and the direct usage of the MySQL connectors.
When users want a forum, a wiki, a helpdesk, a blog, etc. and it's in PHP, chances are it doesn't have a PostgreSQL backend. And if you have to have MySQL, and MySQL works for everything (for some definition of the word "works") while PostgreSQL doesn't... there's your answer.
The real reason is: PostgreSQL doesn't have any must-have apps that only run PGSQL (which is a good thing), and MySQL does (which is a bad thing) so MySQL wins.