Novel optically active ethynyl monomers were synthesized from L-valine and N-methyl-L-valine, and polymerized with a rhodium catalyst to provide the polymers with number-average molecular weights over 200,000 in good yields. The CD and UV-vis spectra of the polymers indicated that they took helical structures with predominantly one-handed screw sense in solution. The polymers served as catalysts of asymmetric reduction of aromatic ketimines to afford optically active amines in moderate yields. (C) 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 4971-4981, 2009