Disclosed are organic-inorganic hybrid self-assembled multilayers that can be used as electrically insulating (or dielectric) materials. These multilayers generally include an inorganic primer layer and one or more bilayers deposited thereon. Each bilayer includes a chromophore or “π-polarizable” layer and an inorganic capping layer composed of zirconia. Because of the regularity of the bilayer structure and the aligned orientation of the chromophore resulting from the self-assembly process, the present multilayers have applications in electronic devices such as thin film transistors, as well as in nonlinear optics and nonvolatile memories.