The new type of catalysts designed for the olefin derivatives polymerization has been synthetized. The novel catalysts are chromium(III) salt type complexes composed of both organic cation and anion, i.e. [Cr(dipic)2][Cr(bipy)(dipic)H2O]∙2H2O and [Cr(dipic)2]Hdmbipy∙2.5 H2O. The compositions of these complexes have been confirmed by a number of instrumental methods including NMR, IR, UV-Vis, MS and elemental analysis ones. Moreover, the crystal structures of these novel catalysts were determined and reported. Furthermore, the [Cr(dipic)2][Cr(bipy)(dipic)H2O]∙2H2O and [Cr(dipic)2]Hdmbipy∙2.5H2O complexes have been studied towards their catalytic activity, after the activation by MMAO (modified methylaluminoxane), in the case of 2-chloro-2-propen-1-ol polymerization at 21 °C and atmospheric pressure. It has been found that novel catalysts, [Cr(dipic)2][Cr(bipy)(dipic)H2O]∙2H2O and [Cr(dipic)2]Hdmbipy∙2.5 H2O, exhibit a very high catalytic activity in the process of the polymerization of the beta-olefin derivatives. The products of a such catalyzed polymerization are the poly(allyl alcohol) derivatives.