Using the C or C++ API detailed in the documentation, write a small program to convert the libconfig format file to either JSON or XML (or if you're feeling adventurous, PHP's serialisation format) and then use the PHP libraries to deal with that output. If the file hasn't changed, you could even cache the converted form.
You can call external programs from PHP and get the output using exec().
The best solution would of course be to write PHP bindings for the library, but depending on how important this library is to your application, that is likely not worth it.
Looking at the format, I would not recommend attempting to use regular expressions to parse the file.