A clay-metal complex multilayer film was prepared by the Langmuir-Blodgett technique. A monolayer of an amphiphilic ruthenium(II) complex, [Ru(phen)(2)(dC18bpy)](ClO4)(2) (phen = 1,10-phenanthroline, dC18bpy = 4,4＇-dioctadecyl-2,2＇-bipyridyl), was formed on an aqueous suspension of hectorite clay (Li-HT). The monolayer acted as a template for adsorption of a clay particle. A hybrid monolayer of a clay and a metal complex was transferred onto a hydrophilic glass plate to form a Z-type multilayer film. X-ray diffraction, UV-visible and FT-IR absorption spectra, and Brewster angle and atomic force microscopic (AFM) measurements confirmed the formation of an ordered film of [Ru(phen)(2)(dC18bpy)](2+)/hectorite with the layer thickness of 5.4 nm.