Readabillity.
If you do it properly (via Setting.settings in your project, under properties in the Solution Explorer) then you can use readable code, such as
string imagePath = Properties.Settings.Default.imagePath;
...
Properties.Settings.Default.imagePath = @"D:\Temp\MyImage.jpg";
Properties.Settings.Default.Save();
With each setting kept separate from each other. The framework then deals with the actual settings file, storing data in XML, instead of you having to make sure it is in teh right place, etc., etc.