like this

Private Sub Form1_Load(ByVal sender As System.Object, ByVal e As System.EventArgs) Handles MyBase.Load
ListView1.View = View.List
Dim i As Integer
For i = 0 To 300
ListView1.Items.Add(i.ToString)
Next i
End Sub

Private Sub ListView1_Click(ByVal sender As Object, ByVal e As System.EventArgs) Handles ListView1.Click
MessageBox.Show(ListView1.FocusedItem.Index.ToString)
End Sub

I had to experiment a little but this pops up a message box with the index number of the item you click on.

hope this helps