Novel optically active poly(phenyleneethynylene-aryleneethynylene)s bearing hydroxy groups with various arylene units [poly(1–2), poly(1–3a), poly(1–3b), poly(1–4)] were synthesized by the Sonogashira–Hagihara coupling polymerization of (S)-3,5-diiodo-4-hydroxy-C6H4CONHCH(CH3)COOC12H25 (1) with HC≡C–Ar–C≡CH [2 (Ar = 1,4-phenylene), 3a (Ar = 2,7-naphthylene), 3b (Ar = 1,4-naphthylene) and 4 (Ar = 1,6-pyrenylene), and the optical properties were compared. Polymers with number-average molecular weights (Mn) of 5,300–11,300 were obtained in 88–94% yields. CD and UV–vis spectroscopic analysis revealed that all the polymers formed predominantly one-handed helical structures in THF. The order of absorption maxima (λmax) of the polymers was poly(1–3a) < poly(1–2) < poly(1–3b) < poly(1–4). Poly(1–2), poly(1–3a), poly(1–3b), and poly(1–4) emitted blue, purplish blue, green and yellow fluorescence, respectively.