The palladium-catalyzed three-component coupling polymerization of p-bromophenylallene and a chiral nucleophile, sodium di-(-)-menthyl methylmalonate, was carried out to give a derivative of poly(p-phenylene-vinylene) having chiral substituents on each vinylene unit. For example, a polymer (M-n=4800, M-w/M-n=1.6) was obtained in a high yield by the polymerization in 1,4-dioxane at 80 degrees C for 24 h in the presence of Pd-(OAc)(2)/4P(o-tolyl)(3) catalyst. The obtained polymer is soluble in common organic solvents and supposed to have a single-handed helical conformation on the basis of its circular dichroism (CD) spectrum which exhibited a clear Cotton effect within the range of its transition absorption (lambda=250 - 400 nm). The nature of the chiral higher-order structure of the polymer was studied in detail by the dependence of the CD spectra of the polymer on the molecular weight and on the character of the solvents.