The Sonogashira-Hagihara coupling polymerization of D-hydroxyphenylglycine-based diiodo monomers 1 and 2 with p-diethynylbenzene gave novel optically active poly(phenyleneethynylene)s 3 and 4 bearing perylene moieties with number-average molecular weights (M-n's) of 4800 and 3700 in 39% and 57% yields. The CD and UV-vis spectroscopic analysis revealed that polymer 3 formed folded helical structures in various solvents, while polymer 4 did not. UV-vis and fluorescence spectroscopic analysis indicated the presence of energy transfer from the phenyleneethynylene main chain to perylene side chains.