Homo- and copolymerizations of chiral amino acid-based N-propargylamides, i.e., N-(tert-butoxycarbonyl)-L-alanine N-t-propargylamide (LA) and N-(trifluoroacetyl)-L-valine N-t-propargylamide (FLV), were conducted with (nbd)Rh+[eta(6)-C6H5B-(C6H5)(3)] as a catalyst to afford the corresponding copolymers with moderate molecular weights in good yields. The CD and UV-Vis spectra showed that poly(LA) and poly(FLV) take helical structures with predominantly one-handed helices, whose CD signs are opposite. The helices of the homopolymers could be tuned by temperature and solvent. The specific rotation, CD and UV-Vis spectra showed that some of the copolymers underwent temperature- and solvent-induced helix inversion. (c) 2005 Elsevier Ltd. All rights reserved.