.cs
DataSet ds = new DataSet();
ds.ReadXml(@Server.MapPath("~/App_Data/Users.xml"));
DataView dv = new DataView(ds.Tables[0]);
foreach (DataRowView drv in dv)
{
this.DropDownList1.Items.Add(new ListItem(drv["UserName"].ToString(), drv["UserID"].ToString()));
}
.xml
<?xml version="1.0" encoding="utf-8"?>
<NewDataSet>
<UserTable>
<UserID>1</UserID>
<UserName>Csaspx</UserName>
</UserTable>
<UserTable>
<UserID>2</UserID>
<UserName>Jacky</UserName>
</UserTable>
<UserTable>
<UserID>3</UserID>
<UserName>Wstime</UserName>
</UserTable>
</NewDataSet>