@ Ian

Using the form re-size event worked perfectly. I ran into a small hiccup with col1. As the form widened col1 did not expand to reveal the rest of it's value. I corrected this but setting it's width to -1 (width of widest value). This caused it to look goofy however when it's value was 0. To correct this I just added an If statement stating that when listview items count is equal to 0/nothing that the columns be set to a numeric value rather than -1 & -2.

Code:
    Private Sub AddLVHeaders()
        Dim colHeaders() As ColumnHeader = {New ColumnHeader With {.Text = "File Name", .Width = -1, .TextAlign = HorizontalAlignment.Left},
                                            New ColumnHeader With {.Text = "File Type", .Width = -2, .TextAlign = HorizontalAlignment.Right}}
        ListView1.Columns.Clear()
        ListView1.Columns.AddRange(colHeaders)

        If ListView1.Items.Count = 0 Then
            Dim colHeaders_alt() As ColumnHeader = {New ColumnHeader With {.Text = "File Name", .Width = 306, .TextAlign = HorizontalAlignment.Left},
                                    New ColumnHeader With {.Text = "File Type", .Width = -2, .TextAlign = HorizontalAlignment.Right}}
            ListView1.Columns.Clear()
            ListView1.Columns.AddRange(colHeaders_alt)
        End If

    End Sub
    Private Sub Form1_Resize(ByVal sender As System.Object, ByVal e As System.EventArgs) Handles MyBase.Resize
        AddLVHeaders()
    End Sub
Thank you again Ian

Resolved