To overcome the defects of the thermal instability of azobenzene, a series of novel photochromic, chiral, liquid-crystalline monomers and polymers were synthesized from (+)-camphor. The copolymerization of the photochromic monomers with comonomers was carried out. The synthesized monomers and polymers were identified with nuclear magnetic resonance, Fourier transform infrared, and elemental analysis. The composition of the copolymers was estimated with elemental analysis. The specific rotation of the chiral compounds and polymers was evaluated. The thermal stability and phases of the polymers during heating and cooling cycles were studied with differential scanning calorimetry and thermogravimetric analysis. The phases of the polymers were identified with polarized optical microscopy textures and X-ray diffraction analysis. The distance between the layers of smectic liquid crystals was estimated from the diffraction angles. Photoisomerization of the configurational E/Z structures was investigated with an ultraviolet-visible spectrophotometer with 300-nm ultraviolet irradiation. The thermal stability of the Z-structural segment in the polymers was confirmed through the heating of the polymer at 70 degrees C for over 10 h. The photoisomerization and thermal stability of the C=C bond in the polymeric materials were demonstrated through a series of novel chiral polymers synthesized in this investigation. Both the polarity of the center part and the molecular length at the ends of the molecules were found to be necessary factors for the formation of liquid-crystalline molecules. (c) 2007 Wiley Periodicals, Inc.