The metal polymers based on mono- and heteroligand β-diketonate complexes of Yb(III) with 2,7-dimethyl-octen-1-dione-3,5, 2,6-dimethyl-heptene-1-dione-3, 5 and with phenanthroline was synthesized. It has been defined that the coordination environment of the central ion remains unchanged during radical polymerization. The shape and position of the bands in the electronic absorption spectra are similar to the corresponding monomeric β-diketonate metal complexes, and slight shifts indicate deformation of the elementary unit of the metal polymer during the formation of the polymer chain. It is shown that the polymerization process lead to an increasing in the thermal stability of polymer complexes in comparison with monomeric analogues. An increase in the emission of metal polymers in comparison with monomeric complexes was established by the method of luminescent spectroscopy, which is due to energy, steric, and structural-mechanical factors.