An electrostatic self-assembly method of fabricating electrostrictive and piezoelectric thin film assemblies not only provides a thinner film than is attainable by conventional methods, but provides excellent molecular-level uniformity and precise structural control, and thus large, effective piezoelectric coefficients. The method produces a thin film assembly including (a) a substrate, and (b) a film having one or a plurality of layers disposed upon the substrate, wherein at least one of the layers includes a dipolar material, and this layer of dipolar material has a uniform thickness of at most 500 nm.