A good reference on the subject is here MSDN. States that you have an Icon for the Application (Desktop Icon), and one for each Window.
A WPF window always displays an icon. When one is not provided by setting Icon, WPF chooses an icon to display based on the following rules:
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Use the assembly icon, if specified.
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If the assembly icon is not specified, use the default Microsoft Windows icon.
Community Content Reference:
“A liitle tip : if you set the application icon and expect to see it on the window – it wont show up if running in debug from VS. Running externally or without attaching (ctrl + f5) the icon displays as expected.”