A fluorescence probe study, surface tension and dye solubilization tests indicate that the water-soluble calixarene, 5,11,17,23,29,35,41,47-octosulfonato-49,50,51,52,53,54,55,56-octododecyloxycalix[8]arene (1(8)-C-12) acts as a "unimolecular'' micelle in water. By forming guest-host-type complexes with 1(8)-C-12, lipophilic dyes, such as methyl yellow (MY), p-hydroxyazobenzene (HAB) and 1-(p-phenylazophenylazo)-2-naphthol (Sudan III), dissolve in aqueous solution. By dipping a charged substrate in the 1(8)-C-12-dye solution and a cationic polyelectrolyte solution alternately, these small molecular dyes were successfully self-assembled into multilayer films.