Zirconium octadecylphosphonate monolayer and multilayered films have been prepared and characterized by Brewster angle microscopy (BAM), attenuated total reflection-Fourier transform IR spectroscopy, ellipsometry, X-ray diffraction and X-ray photoelectron spectroscopy (XPS). BAM data reveal the rigid nature of a Langmuir monolayer of octadecylphosphonic acid compressed on a Zr4+ ion subphase; therefore a deposition procedure combining Langmuir-Blodgett (LB) and self-assembly techniques has been developed. First, an octadecylphosphonic acid organic template is prepared by the LB technique and then Zr4+ ions are self-assembled onto the template from solution. Finally, a capping layer of octadecylphosphonic acid is transferred to the zirconated template to complete the bilayer assembly. The asymmetric methylene stretch frequency v(a)(CH2) appears at 2918 cm-1 and possesses a full width at half-maximum of 20 cm-1 for the template layer, a bilayer and a multilayered film. The position and width of the v(a)(CH2) band indicates that close-packed well-ordered films are formed. Ellipsometry demonstrates a layer-by-layer deposition in multilayered films, while X-ray diffraction proves that the films are indeed layered, possessing a d spacing of 52 angstrom. XPS analysis of the template layer shows a Zr:P ratio of 1:1 within 10% error, while the bilayer and multilayered films possess a Zr:P ratio of 1:2 consistent with the stoichiometry of the bulk zirconium phosphonates.