Chiral polyepichlorohydrin was obtained as a crystalline, optically active powder by coordinative polymerization of S(+)-epichlorohydrin. Subsequent reaction with lithium diphenylphosphide in THF resulted in substitution of about 90% of the chlorine atoms by the P(C6H5)2 group to give an insoluble polymer, which was characterized by elemental analysis, 31P CP MAS NMR, and IR spectroscopy. On addition of solutions of bis(1.5-cyclooctadiene)-rhodium tetrafluoroborate to the polymer “heterogenization” of the complex occurred. The reason for the as yet short operational life time during the hydrogenation of α-acetamido cinnamic acid is the leaching of the metal complex moiety. The rhodium atom is coordinated to only one phosphorus atom of the polymer in the side group and rather weakly to one oxygen atom of the polymer chain.