A novel poly(phenylacetylene) derivative bearing optically active pyrene moieties as the pendant groups (poly-(R)-1) was prepared by the polymerization of the corresponding monomer (R)-1 in the presence of a rhodium catalyst, and its chiroptical property was investigated. Poly-(R)-1 exhibited an induced circular dichroism (ICD) in the polymer backbone region due to the predominantly one-handed helical conformation. The ICD pattern dramatically changed and was accompanied by inversion of the Cotton effect sign in response to a change in the temperature and solvent, indicating that poly-(R)-1 underwent a helix-helix transition in response to the external stimuli.