To illustrate the problem you are having, let's look at some code...
Dictionary<string, string> test = new Dictionary<string, string>();
test.Add("Key1", "Value1"); // Works fine
test.Add("Key2", "Value2"); // Works fine
test.Add("Key1", "Value3"); // Fails because of duplicate key
The reason that a dictionary has a key/value pair is a feature so you can do this...
var myString = test["Key2"]; // myString is now Value2.
If Dictionary had 2 Key2's, it wouldn't know which one to return, so it limits you to a unique key.