Chiral poly(alkyl phenylpropiolate)s -{(C6H5)C=C[CO2(CH2)(2)OCOR*]}(n)-with R* = (S)(+)-[1-(6-methoxy-2-naphthyl)ethyl (P1), (1R,2S,5R)-(-)-menthoxymethyl (P2), (S)-(+)-(alpha-acetoxy)benzyl (P3), and cholesteryloxy (P4) were synthesized, and their structures and properties were investigated. The monomers [C6H5C-CCO2(CH2)(2)OCOR*; 1-4] were prepared by esterifications of stereogenic acids 8-10 or chloroformate (11) with 3-hydroxyethyl phenylpropiolate (7) in high yields. Polymerizations of 1-4 were effected by MoCl5-Ph4Sn at 60 or 80 degreesC, and polymers with high molecular weights (M-w up to similar to100 X 10(3)) were obtained in moderate yields. The polymers were characterized by IR, NMR, TGA, UV, and CD analyses. All of the polymers are stable, losing little of their weights when heated to greater than or equal to 300 degreesC and undergoing no chain scissions when annealed in air at greater than or equal to 150 degreesC. The macromolecular chains take helical conformations with preferred handedness, and their helical chirality can be reversibly tuned by solvent or temperature to varying extents.