I also once worked on an app which used PHP4's XML support quite heavily, and would have required quite a bit of work to move to PHP5.

One of the other significant changes I was looking at at the time was the change of the default handling of function parameters. In PHP4 if I remember, they were pass-by-copy unless you specified otherwise, but in PHP5 is changed to pass-by-reference by default. In well written code, that probably won't make a big difference to you, but it could certainly cause problems.

I think one other thing I found changed is that objects are no longer allowed to overwrite their 'this' field. I would say that was a really bad idea to begin with (and I think it may have not been an intentional feature in PHP4), but I certainly found a few parts of our system that relied on it.

Hope some of that helps.