The layer-by-layer growth of film structures consisting of sequential depositions of oppositely charged polymers and macrocycles (ring-shaped molecules) have been constructed using molecular self-assembly techniques. These self-assembled thin films were characterized with X-ray reflectometry, which yielded (1) the average electron density, (2) the average thicknesses, and (3) the roughness of the growth surface of the self-assembled multilayer of macrocycles and polymers. These observations suggest that inorganic-organic interactions play an important role during the initial stages of thin-film growth, but less so as the thin film becomes thicker. Optical absorption techniques were also used to characterize the self-assembled multilayers. Phorphyrin and phthalocyanine derivatives were chosen as the building blocks of the self-assembled multilayers because of their interesting optical properties.