Description:
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From manual page: http://www.php.net/configuration.file
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Bullet 3 should read:

As of PHP 5.2.0, the location of the php.ini file can be set for different versions of PHP. The following registry keys are examined in order: [HKEY_LOCAL_MACHINE\SOFTWARE\WOW6432Node\PHP\x.y.z], [HKEY_LOCAL_MACHINE\SOFTWARE\WOW6432Node\PHP\x.y] and [HKEY_LOCAL_MACHINE\SOFTWARE\WOW6432Node\PHP\x], where x, y and z mean the PHP major, minor and release versions. If there is a value for IniFilePath in any of these keys, the first one found will be used as the location of the php.ini (Windows only).
[HKEY_LOCAL_MACHINE\SOFTWARE\WOW6432Node\PHP], value of IniFilePath (Windows only). 

Summery:
Keys for 32bit binaries are stored under HKEY_LOCAL_MACHINE\SOFTWARE\WOW6432Node\
Keys for 64bit binaries are stored under HKEY_LOCAL_MACHINE\SOFTWARE\

Test script:
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<?php echo phpinfo(1);

Expected result:
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Loaded Configuration File shows the file that is loaded.