A novel, optically active, cis-transoidal poly(phenylacetylene) bearing an L-proline residue as the pendant group () was prepared by the polymerization of the corresponding monomer using a rhodium catalyst in water, and its chiroptical property was investigated using circular dichroism spectroscopy. showed intense Cotton effects in the UV–visible region of the polymer backbone in water, resulting from the prevailing one-handed helical conformation induced by the covalent-bonded chiral L-proline pendants and exhibited a unique helix-sense inversion in response to external, achiral, and chiral stimuli, such as the solvent and interactions with chiral small molecules. We found that could enantioselectively trap 1,1′-2-binaphthol within its hydrophobic helical cavity inside the polymer in aqueous media and underwent an inversion of its helical sense in the presence of one of the enantiomers. The effect of the optical purity of 1,1′-2-binaphthol on the chiroptical properties of was also investigated. Chirality 23:35–42, 2011 © 2011 Wiley Periodicals, Inc.