Helical R/S-poly(urethane urea)s (R/S-HPUUs) were synthesized successfully with R/S-1,1'-binaphthyl-2',2-diol, toluene 2,4-diisocyanate, and 1,4-diaminobenzene by a simple hydrogen-transfer addition reaction. The structure and optical properties of R/S-HPUUs were investigated systematically with Fourier transform infrared spectroscopy, H-1-NMR spectra, absorption and circular dichroism, thermogravimetry, differential scanning calorimetry, and X-ray diffraction measurements. Fourier transform infrared spectra showed that all the -NH and carbonyl groups in R/S-HPUUs were hydrogen-bonded. R-HPUU and S-HPUU were two enantiomorphs with wonderful mirror-image symmetry according to circular dichroism spectroscopy analysis. exhibited optical activity, and the optical rotations were +54.7 and -60.7 degrees, respectively. R/S-HPUUs showed excellent thermal stability because of the plane-bifureated interchain hydrogen bonds and helical stereostructures according to thermogravimetry differential scanning calorimetry, and X-ray diffraction analysis. Moreover, the left-handed rotation was more stimulative for the construction of hydrogen bonds than the right-handed rotation, so S-HPUU showed higher thermal stability and better crystallizability. (C) 2008 Wiley Periodicals, Inc. J Appl Polym Sci 111: 2134-2140, 2009