Photoactive nanostructured micellar films were prepared from the amphiphilic copolymer poly(sodium styrene-sulfonate-stat-2-vinyl naphthalene) (PSSS-stat-VN) and cationic polyelectrolyte poly(diallyldimethylammonium chloride) (PDADMAC) or poly(allylamine hydrochloride) (PAH) on quartz and silicon substrates via layer-by-layer (LbL) electrostatic self-assembly. The macromolecules of this amphiphilic copolymer adopt a coiled micellar conformation in aqueous solution that is preserved in the films as evidenced by atomic force microscopy (AFM) and spectroscopic studies. The hydrophobic domains present in the film can serve as host sites for various organic molecules. The probe molecules reside in those isolated nanosize domains. Their aggregation and quenching of their emission is eliminated. The experiments showed a regular growth of multilayer thickness and the content of solubilized compounds in the films. Thus, a defined amount of the hydrophobic compounds of interest may be introduced into these water-processable polymeric films. Some stratification of the films was induced by the presence of stiff nanoparticle-like micelles. That makes these films an important new material for studies of photoinduced energy and electron transfer.