Grazie a tutti per i vari "contributi" 
Sono riuscita a risolvere così:
codice:
Dim sel As String = ListView1.SelectedValue
Dim conn As New SqlConnection()
conn.ConnectionString = "Data Source=.\SQLEXPRESS;AttachDbFilename=|DataDirectory|\Database.mdf;Integrated Security=True;User Instance=True"
Dim SelMatricola As SqlCommand = New SqlCommand("SELECT * FROM [PostIt] WHERE ([IdPostIt] = @sel)", conn)
Dim MailPar As New SqlParameter("@sel", SqlDbType.NVarChar)
SelMatricola.Parameters.Add(MatrPar)
MatrPar.Value = ListView1.SelectedValue
conn.Open()
Dim reader As SqlDataReader = SelMatricola.ExecuteReader()
If reader.HasRows = True Then
Do While reader.Read()
Matr.Text = reader.Item(3).ToString
Loop
End If
reader.Close()
conn.Close()