Like that you can set DataTextField and DataValueField of DropDownList using "Key" and "Value" texts :
Dictionary<string, string> list = new Dictionary<string, string>();
list.Add("item 1", "Item 1");
list.Add("item 2", "Item 2");
list.Add("item 3", "Item 3");
list.Add("item 4", "Item 4");
ddl.DataSource = list;
ddl.DataTextField = "Value";
ddl.DataValueField = "Key";
ddl.DataBind();