Justin has posted a few cool things that you can do by combining PHP with someof the Windows functionality PHP has access to (either via direct function calls or through the COM object).
Many PHP examples out there are designed for a linux/unix operating system. I am going to give some examples of some interesting functionality that only works with php running in a windows environment (IIS or apache).
Hist list includes little things like ejecting the CD-ROM and sending things to the printer out to working with the registry and listing the current system processes.