Multiple values for a single config key

Try

<add key="mykey" value="A,B,C"/>

And

string[] mykey = ConfigurationManager.AppSettings["mykey"].Split(',');

I know I'm late but i found this solution and it works perfectly so I just want to share.

It's all about defining your own ConfigurationElement

namespace Configuration.Helpers
{
    public class ValueElement : ConfigurationElement
    {
        [ConfigurationProperty("name", IsKey = true, IsRequired = true)]
        public string Name
        {
            get { return (string) this["name"]; }
        }
    }

    public class ValueElementCollection : ConfigurationElementCollection
    {
        protected override ConfigurationElement CreateNewElement()
        {
            return new ValueElement();
        }


        protected override object GetElementKey(ConfigurationElement element)
        {
            return ((ValueElement)element).Name;
        }
    }

    public class MultipleValuesSection : ConfigurationSection
    {
        [ConfigurationProperty("Values")]
        public ValueElementCollection Values
        {
            get { return (ValueElementCollection)this["Values"]; }
        }
    }
}

And in the app.config just use your new section:

<configSections>
    <section name="PreRequest" type="Configuration.Helpers.MultipleValuesSection,
    Configuration.Helpers" requirePermission="false" />
</configSections>

<PreRequest>
    <Values>
        <add name="C++"/>
        <add name="Some Application"/>
    </Values>
</PreRequest>

and when retrieving data just like this :

var section = (MultipleValuesSection) ConfigurationManager.GetSection("PreRequest");
var applications = (from object value in section.Values
                    select ((ValueElement)value).Name)
                    .ToList();

Finally thanks to the author of the original post

The config file treats each line like an assignment, which is why you're only seeing the last line. When it reads the config, it assigns your key the value of "A", then "B", then "C", and since "C" is the last value, it's the one that sticks.

as @Kevin suggests, the best way to do this is probably a value whose contents are a CSV that you can parse apart.