An ionically self-assembled monolayer (ISAM) technique for thin-film deposition has been employed to fabricate materials possessing the noncentrosymmetry that is requisite for a second-order, χ(2), nonlinear optical response. As a result of the ionic attraction between successive layers, the ISAM χ(2) films self-assemble into a noncentrosymmetric structure that has exhibited no measurable decay of χ(2) at room temperature over a period of more than one year. The second-harmonic intensity of the films exhibits the expected quadratic dependence on film thickness up to at least 100 bilayers, corresponding to a film thickness of 120 nm. The polarization dependence of the second-harmonic generation yields a value of 35° for the average tilt angle of the nonlinear optical chromophores away from the surface normal. © 1999 American Institute of Physics.