Langmuir-Blodgett (LB) films of zirconium salts of the functionalized phosphonic acids 4-octadecyloxyphenylphosphonic acid (P0), 4-octadecyloxybiphenylphosphonic acid (B0), and 4-(4-octadecyloxyphenyldiazenyl)phenylphosphonic acid (A0) have been prepared and characterized. Layers of P0, B0, or A0 can be deposited onto zirconated octadecylphosphonic acid layers using a three-step deposition procedure to form alternating zirconium phosphonate LB bilayers. Film composition and molecular orientations are characterized through X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), and Fourier transform infrared spectroscopy (FTIR).