Firstly I set the Multi Select to false....
Private Sub ListView1_SelectedIndexChanged(ByVal sender As System.Object, ByVal e As System.EventArgs) Handles ListView1.SelectedIndexChanged
With Me.ListView1
Dim i As Integer
For Each item As ListViewItem In ListView1.SelectedItems
i = item.Index
Next
Dim innercounter As Integer = 0
For Each subItem As ListViewItem.ListViewSubItem In ListView1.Items(i).SubItems
Dim myString As String = ListView1.Items(i).SubItems(innercounter).Text
Select Case innercounter
Case 1
TextBox1.Text = myString
Case 2
TextBox2.Text = myString
Case 3
TextBox3.Text = myString
Case 4
TextBox4.Text = myString
Case 5
TextBox5.Text = myString
End Select
innercounter += 1
Next
End With
End Sub