See also the migration guides for PHP versions 5.1.x and 5.2.x.
PHP 5 and the integrated Zend Engine 2 have greatly improved PHP's performance and capabilities, but great care has been taken to break as little existing code as possible. So migrating your code from PHP 4 to 5 should be very easy. Most existing PHP 4 code should be ready to run without changes, but you should still know about the few differences and take care to test your code before switching versions in production environments.