It doesn't work for some PHP statements, although it seems to work for most of the things that 'matter' where a bit of assistance might be required.
One possibility is that PhpED uses the information that is provided by PHP Reflection
http://www.php.net/manual/en/intro.reflection.php, and maybe PHP does not provide information on some words. Maybe require_once() is a statement, isset() is a function and file_exists() is from a class, so only file_exists() gets code completion. However, I don't know if PhpED uses Reflection or not.