Here's a macro that has no problem adding 64K items to a collection although
it takes a minute or so to run. Perhaps your dataset had 256 unique values
and no more, so it was capping there. I commented out the key assignment in
the test macro, but it would work uncommented too since all the values
generated below are unique.
Sub CollectionTester()
Dim coll As Collection, n As Long
Dim cell As Range
' Create a list of values all the way down col A
For Each cell In Range("A1:A65536")
cell.Value = cell.Address(0, 0)
Next
' Add to the collection every value in the list
Set coll = New Collection
For Each cell In Range("A1:A65536")
coll.Add cell.Value ', cell.Value ' Optional
Next
' Loop through the collection and
' put the values in column 2
For n = 1 To coll.Count
Cells(n, 2).Value = coll(n)
Next
Set coll = Nothing
End Sub