Multilayer thin films consisting of anionic alpha-zirconium phosphate (alpha-ZrP) sheets, tetrameric zirconium hydroxide cations [Zr-4(OH)(8)(H2O)(16)](8+) (Zr-4(8+)), and alkanediylbis(phosphonic acid) (C(N)BPA) have been grown on silicon and gold surfaces by sequential adsorption reactions. The thin films were characterized by ellipsometry, X-ray diffraction, reflectance infrared spectroscopy, X-ray photoelectron spectroscopy (XPS), and atomic force microscopy(AFM). Alternately dipping cationic substrates into exfoliated alpha-ZrP-containing suspensions, aqueous zirconium oxychloride, and ethanolic C(16)BPA solutions generates a mixed ionic/covalent multilayer structure. The tetrameric Zr-4(8+) cation adsorbs onto the alpha-ZrP surface, providing a covalent anchoring point for the growth of the C(16)BPA layer. Adsorbing a second layer of zirconium ions onto the C(16)BPA layer allows one to continue the layer growth sequence using either covalent (metal/phosphonate) or ionic (alpha-ZrP/polycation) interlayer connections. A multilayer film with a repeating alpha-ZrP/Zr-4(8+)/C(16)BPA/Zr-4(8+) sequence is sufficiently well-ordered in the stacking direction to give a Bragg peak in the diffraction pattern. The intensities of infrared absorbances in the symmetric and asymmetric C-H stretching regions, which arise from C(16)BPA, are linear with the C(16)BPA layer number. This "mix and match" approach provides a versatile means of assembling multilayer heterostructures from both ionic and covalent building blocks, with essentially any desired sequence of layers.