A multilayer film was deposited by molecular deposition onto aminopropylsilanated silicon or quartz through the alternate salt-forming reaction of a monester of polymaleic acid containing an azobenzene-sulphonic salt side chain and a bipolar quaternary ammonium bearing biphenyl mesogenic group. UV-visible and polarized UV-visible spectra were employed to study the growing process and the aggregation of chromophore. A well-ordered superlattice structure was identified by X-ray diffraction.