Achiral phenylacetylene monomers were polymerized using a rhodium (Rh) complex catalyst in the presence of (S)1-phenylethylamine. Addition of copper(I) iodide (CuI) into the catalytic system improved the polymer yield. The monomer, which had two hydroxy groups and a hydrogalvinoxyl unit, gave the corresponding polymer with an optically active helical conformation stabilized by intramolecular hydrogen bonding. The chemical oxidation of the polymer yielded the corresponding optically active helical polyradical with high spin concentration.