How to get a List<string> collection of values from app.config in WPF?

You could have them semi-colon delimited in a single value, e.g.

App.config

<add key="paths" value="C:\test1;C:\test2;C:\test3" />

C#

var paths = new List<string>(ConfigurationManager.AppSettings["paths"].Split(new char[] { ';' }));

You can create your own custom config section in the app.config file. There are quite a few tutorials around to get you started. Ultimately, you could have something like this:

<configSections>
    <section name="backupDirectories" type="TestReadMultipler2343.BackupDirectoriesSection, TestReadMultipler2343" />
  </configSections>

<backupDirectories>
   <directory location="C:\test1" />
   <directory location="C:\test2" />
   <directory location="C:\test3" />
</backupDirectories>

To complement Richard's answer, this is the C# you could use with his sample configuration:

using System.Collections.Generic;
using System.Configuration;
using System.Xml;

namespace TestReadMultipler2343
{
    public class BackupDirectoriesSection : IConfigurationSectionHandler
    {
        public object Create(object parent, object configContext, XmlNode section)
        {
            List<directory> myConfigObject = new List<directory>();

            foreach (XmlNode childNode in section.ChildNodes)
            {
                foreach (XmlAttribute attrib in childNode.Attributes)
                {
                    myConfigObject.Add(new directory() { location = attrib.Value });
                }
            }
            return myConfigObject;
        }
    }

    public class directory
    {
        public string location { get; set; }
    }
}

Then you can access the backupDirectories configuration section as follows:

List<directory> dirs = ConfigurationManager.GetSection("backupDirectories") as List<directory>;

There's actually a very little known class in the BCL for this purpose exactly: CommaDelimitedStringCollectionConverter. It serves as a middle ground of sorts between having a ConfigurationElementCollection (as in Richard's answer) and parsing the string yourself (as in Adam's answer).

For example, you could write the following configuration section:

public class MySection : ConfigurationSection
{
    [ConfigurationProperty("MyStrings")]
    [TypeConverter(typeof(CommaDelimitedStringCollectionConverter))]
    public CommaDelimitedStringCollection MyStrings
    {
        get { return (CommaDelimitedStringCollection)base["MyStrings"]; }
    }
}

You could then have an app.config that looks like this:

<?xml version="1.0" encoding="utf-8" ?>
<configuration>
  <configSections>
    <section name="foo" type="ConsoleApplication1.MySection, ConsoleApplication1"/>
  </configSections>
  <foo MyStrings="a,b,c,hello,world"/>
</configuration>

Finally, your code would look like this:

var section = (MySection)ConfigurationManager.GetSection("foo");
foreach (var s in section.MyStrings)
    Console.WriteLine(s); //for example