The VB6 ListBox control does not have a method to determine if it already contains a given value. You will have to use the List() and ListCount properties of the ListBox to do a search. If the ListBox has Sorted=True, you can use a binary search pattern; otherwise it will have to be a sequential search.
I am assuming that you are populating the items via AddItem, and not data bindings (DataSource, DataField etc.). If you are using data bindings, then you will need to work on the SQL, and perhaps use DISTINCT, as jworrin has recommended.