The Sm(III) complexes with 2-methyl-5-phenylpenten-1-3,5-dione and their phenanthroline adduct were synthesized. The polycomplexes on their basis and copolymers with styrene and methylmethacrylate at different ratios of monomers were obtained by free-radical polymerization. The results of above studies have shown that the configuration of the chelate unit is unchanged during the polymerization. As a result, the type of coordination was determined and the structure of coordination polyhedra was assumed. The luminescence spectra of obtained metallocomplexes and polymers in solutions and solid state are investigated and analyzed.