cis-Stereoregular poly(N-propargylcarbamates) [poly(1)-poly(6)] were synthesized by the polymerization of the corresponding monomers [1: (S)-CH=CCH2NHCOOCH(CH3)CH2CH3; 2: (S)-CH&3bond; CCH2NHCOOCH2CH(CH3)CH2CH3; 3: (S)-CH&3bond; CCH2NHCOOCH2CH2CH(CH3)CH2CH3; 4: (S)-CH&3bond; CCH2NHCOOCH2CH2CH2CH(CH3)CH2CH3; 5: (S)-CH&3bond; CCH2NHCOOCH(CH3)CH2CH2CH2CH2CH3; 6: (S)-CH&3bond; CCH2NHCOOCH(CH3)Ph] with a rhodium catalyst. Poly(2)-poly(6) took helical structure stabilized by intramolecular hydrogen bonding. They changed the conformation with temperature and addition of a polar solvent. Effects of the distance between the chiral center and main chain and the phenyl group were examined. H-1 NMR and CD spectroscopic analyses revealed that the closer the distance between the chiral center and main chain, the more stable the helix and the rigid the polymer, i.e., poly(5) > poly(2) > poly(3) > poly(4). When the distance between the chiral center and main chain was the same, the polymer without phenyl groups [poly(5)] was more rigid than the one with phenyl groups [poly(6)], and the helical structure of the former was more stable.