I worked on a project that used XML as document format for config files.
Why use XML when INI files are way easier to read, and especially edit if needs be?
Why add a ton of additional sugar on top of something as simple as "a=b" for config files?
An example of XML config we used at my workplace was a processing pipeline with various modules and options/parameters encoded for each phase (some optional) of the pipeline. So in a sense it was configuration that resulted in executing code modules, not so much your standard options.