You don't need arrays for this. Try something like:
ActiveSheet.Range("$A$1:$A$" & LastRow).RemoveDuplicates Columns:=1, Header:=xlYes
If there's no header, change accordingly.
EDIT: Here's the traditional method, which takes advantage of the fact that each item in a Collection
must have a unique key:
Sub test()
Dim ws As Excel.Worksheet
Dim LastRow As Long
Dim coll As Collection
Dim cell As Excel.Range
Dim arr() As String
Dim i As Long
Set ws = ActiveSheet
With ws
LastRow = .Range("C" & .Rows.Count).End(xlUp).Row
Set coll = New Collection
For Each cell In .Range("C4:C" & LastRow)
On Error Resume Next
coll.Add cell.Value, CStr(cell.Value)
On Error GoTo 0
Next cell
ReDim arr(1 To coll.Count)
For i = LBound(arr) To UBound(arr)
arr(i) = coll(i)
'to show in Immediate Window
Debug.Print arr(i)
Next i
End With
End Sub