How to write an URI string in App.Config

You haven’t properly encoded the ampersands in your URI. Remember that app.config is an XML file, so you must conform to XML’s requirements for escaping (e.g. & should be &, < should be < and > should be >).

In your case, it should look like this:

<appSettings>
    <add
        key="fooUriString" 
        value="https://foo.bar.baz/download/DownloadStream?id=5486cfb8c50c9f9a2c1bc43daf7ddeed&amp;login=null&amp;password=null"
    />
</appSettings>

But in general, if you wanted to store a string that looked like "I <3 angle bra<kets & ampersands >>>" then do this:

<appSettings>
    <add
        key="someString"
        value="I &lt;3 angle bra&lt;kets &amp; ampersands &gt;&gt;&gt;"
    />
</appSettings>

void StringEncodingTest() {
    String expected = "I <3 angle bra<kets & ampersands >>>";
    String actual   = ConfigurationManager.AppSettings["someString"];
    Debug.Assert.AreEqual( expected, actual );
}