Abstract: A method for making a multilayer structure having macroscopic second order nonlinear optical properties is described. The resulting nonlinear optical structures made by the method are also described. The method includes the steps of contacting a substrate having ionic adsorption sites with a first charged polyion; ceasing contact of the substrate with the first charged polyion; and thereafter, contacting the substrate with a second charged polyion having a charge opposite to that of the first charged polyion, wherein at least one of the polyions includes a nonlinear optical chromophoric side chain.