That depends on whether you're using any code/functions deprecated in PHP5.
For instance, if you're parsing XML using DOMXML in PHP4, it has been replaced by DOM in PHP5, and the XML parser will break if moved to PHP5.
But if you're using very common, not-so-groundbreaking stuff like file_get_contents(), or mysql_connect(), etc, then you might not have a problem.
If you're uncertain (and even if you're not, to be safe) I'd suggest you just install the app in a PHP5 testing environment and run through it there to determine what modifications you'll have to make, if any, using any error messages that might show up.