The most important thing to read would be the php.net section on migrating from PHP 4 to PHP 5. Since PHP 5 first came out, they have been moving towards a stricter language (PHP will be in strict mode by default in version 6), so you should expect to see a lot of warnings, if not errors.
There were more backward-compatibility-breaking changes made since PHP 5.0 came out, for completeness you should also read:
Migrating from PHP 5.0.x to PHP 5.1.x
Migrating from PHP 5.1.x to PHP 5.2.x
Migrating from PHP 5.2.x to PHP 5.3.x
I realise that's a lot of reading, but that should be a comprehensive list of everything that could break.