An optically active poly(phenylacetylene), poly{2-(R)-methyl-2-[4'-(tetradecyloxy)biphenyl-4-yloxy]-propyl 4-ethynylbenzoate} (P1) is synthesized in a high yield with a high molecular weight (1.3 x 10(6) g/mol) by [Rh(nbd)Cl](2) catalyst. The chemical structure of the polymer is characterized by IR and NMR spectroscopies with satisfactory analysis data. The polymer is soluble in many common organic solvents. It shows circular dichroism (CD) band in the absorption region of the polyacetylene backbone, indicating that P1 is chiroptical owing to the formation of helical conformation with an excess screw sense. Combining the results of CD and light scattering experiments, we find that addition of poor solvent can induce the neighboring helical segments within a single polymer strand to become closer, resulting in exciton coupling prior to polymer precipitation. The exciton coupling can be kept in the solid state after solvent evaporation. (c) 2008 Elsevier Ltd. All rights reserved.