Here is a bit of code that will populate the comboBox with unique values

Private Sub UserForm_Initialize()
    Dim Rws As Long, Rng As Range, c As Range, y As Integer, x
    Rws = Cells(Rows.Count, "A").End(xlUp).Row
    For y = 1 To Rws
        Set c = Cells(y, 1)
        Set Rng = Range(Cells(1, 1), Cells(y, 1))
        x = Application.WorksheetFunction.CountIf(Rng, c)
        If x = 1 Then ComboBox1.AddItem c
    Next y

End Sub
Unique.jpg