The configuration file (called php3.ini in PHP 3, and simply php.ini as of PHP 4) is read when PHP starts up. For the server module versions of PHP, this happens only once when the web server is started. For the CGI and CLI version, it happens on every invocation.
php.ini is searched in these locations (in order):
SAPI module specific location (PHPIniDir directive in Apache 2, -c command line option in CGI and CLI, php_ini parameter in NSAPI, PHP_INI_PATH environment variable in THTTPD)
HKEY_LOCAL_MACHINE\SOFTWARE\PHP\IniFilePath (Windows Registry location)
The PHPRC environment variable
Current working directory (for CLI)
The web server's directory (for SAPI modules), or directory of PHP (otherwise in Windows)
Windows directory (C:\windows or C:\winnt) (for Windows), or --with-config-file-path compile time option
If php-SAPI.ini exists (where SAPI is used SAPI, so the filename is e.g. php-cli.ini or php-apache.ini), it's used instead of php.ini. SAPI name can be determined by php_sapi_name().
Note: The Apache web server changes the directory to root at startup causing PHP to attempt to read php.ini from the root filesystem if it exists.
The php.ini directives handled by extensions are documented respectively on the pages of the extensions themselves. The list of the core directives is available in the appendix. Probably not all PHP directives are documented in the manual though. For a complete list of directives available in your PHP version, please read your well commented php.ini file. Alternatively, you may find the the latest php.ini from CVS helpful too.
Example 9-1. php.ini example