How do I use the string associated with ValueMember properly?

Hi all & thanks in advance for any help you can give,
 
I'm an absolute beginner with programming and am trying to use the "ValueMember" string of a ComboBox List to set a string value, so I can then use that to send an email.
 
Here's what I've got so far:
 
DataTable table = new DataTable();
DataColumn colName = new DataColumn("Name");
DataColumn colEmailID = new DataColumn("Email");
table.Columns.Add(colName);
table.Columns.Add(colEmailID);
StreamReader reader = new StreamReader(System.Environment.CurrentDirectory + \\Email.txt);
do
{
table.Rows.Add(reader.ReadLine().Split(','));
}
while (reader.Peek() != -1);
cmbRecipient.DataSource = table;
cmbRecipient.DisplayMember = "Name";
cmbRecipient.ValueMember = "Email";
cmbRecipient.SelectedIndex = 0;

 
Ok, this works well at hiding the actual Email from view, but I can't find any way of actually assigning the string of "cmbRecipient.ValueMember", my code appears to only care what is displayed, not the actual value assigned.
 
Here's a few ways I've tried to assign the "cmbRecipient.ValueMember" to my program:
 
//string[] EmailAdd = cmbRecipient.ValueMember;
//string EmailAdd = cmbRecipient.ValueMember;
//string EmailAdd = cmbRecipient.Text;
//string EmailAdd = "Email";
 
None of these seem to work, it just keeps taking what is displayed, not what I've told it in code to set.
 
Any advice would be GREATLY appreciated.
 
Thanks for helping.
Andy