You need to add the System.Configuration reference in your project

App.Config
<?xml version="1.0" encoding="utf-8" ?>
<configuration>
<connectionStrings>
<add name="ConString"
connectionString="Data Source=AZEEM-HP;Initial Catalog=Sample;Integrated Security=True"/>
</connectionStrings>
</configuration>
Add a Button and a Label in your Form. Add OnClick Event for Button.
Code to get the ConnectionString.
C#:
private void button1_Click(object sender, EventArgs e)
{
this.label1.Text = ConfigurationManager.ConnectionStrings["ConString"].ConnectionString;
}
VB.Net
Private Sub button1_Click(ByVal sender As System.Object, ByVal e As System.EventArgs) Handles button1.Click
Me.label1.Text = ConfigurationManager.ConnectionStrings("ConString").ConnectionString
End Sub