The [applicationName].exe.config in your [projectName]\bin\debug directory will contain the default values. So I guess that's the file you're looking for. I belive it's xml, so you can open and check that it contains the values you want.

However, if you change values at runtime, two files may be created depending which kind of value you're changing (user or application). The files may be something like the following:

C:\Document and Settings\[user]\Local Settings\Application Data\[the company from your assembly file]\[application name][Generated key]

C:\Document and Settings\[user]\Application Data\[the company from your assembly file]\[application name][Generated key]

Did that solve it