The advantages of the ionic self-assembled monolayer (ISAM) technique are demonstrated for the fabrication of nan-centrosymmetric thin films of new nonlinear optical (NLO) polymers. Results are presented, e.g., from UV-vis spectroscopy, fluorescence spectroscopy, and second-harmonic generation experiments, that confirm the second-order NLO behavior of these polydye materials. One of the materials is shown to have not only a stronger chi((2)) response-which should not decay over time-but also a higher degree of ordering than commercially available polymers.