The complexes of samarium(III) with 2-methyl-5-phenylpenten-1-3,5-dione (mphpd) Sm(mphpd)(3)2H(2)O and 2,6-dymethyl-heptene-1-3,5-dione (hdmhpd), Sm(hdmhpd)(m) were synthesized. The polycomplexes on their basis [Sm(mphpd)(3)](n), [Sm(hdmhpd)(m)](n) and copolymers with styrene Sm(mphpd)(3)-co-styrene in ratio 5:95 were obtained by free-radical polymerization and the kinetics of polymerization was studied by dilatometric method at the first time. The method of dynamic light scattering and the results of electronic microscopy showed that the obtained polymer systems are nanoscale. The luminescent spectra of obtained metal complexes in solid state are investigated and analyzed. The electroluminescent spectra of organic planar heterostructure ITO/PEDOT:PSS/{[Sm(mphpd)(3)](n)[Styrene](m)}/Al are examined.