A series of novel N-propargylamides carrying dipole azobenzene chromophores were synthesized and polymerized with [Rh(nbd)Cl](2) catalyst to obtain cis-transoid poly(N-propargylamides). The solubility, thermal stability and conformation of these polymers were also studied. The introduction of valeryl group increased the solubility of this kind of poly(N-propargylamides). All the polymers exhibited a good, thermal stability. CD and UV-Vis spectra showed that poly(N-propargylamide) (Poly(V-2b)) took a tight helical structure with predominantly one-handed screw sense. Poly(V-2b) exhibited a good stable helical structure at various temperatures (5-60 degrees C). It also maintained good helicity in polar solvent. The improved helix stability could be attributed to the enhanced hydrogen bonding strength and steric repulsion between the newly designed azobenzene groups. Furthermore, the electrostatic repulsion between the dipole azobenzene chromophores in the side chains improved the helix stability as well. The backbone of Poly(V-2b) still kept helical sense after the isomerization of trans-azobenzene to the cis form under UV irradiation.