Ethyl–cyanoethyl cellulose (E–CE)C/poly (acrylic acid) (PAA) composites were prepared by polymerizing acrylic acid (AA) in (E–CE) C/AA cholesteric liquid crystalline solutions. The morphology and structure and the compatibility of composites prepared in different conditions were studied by small-angle light scattering (SALS), differential scanning calorimetry (DSC), X-ray spectrometry, polarizing microscopy, and electron microscopy. Ho-mogeneous composites with the cholesteric structure could be obtained by photopolymerization. During the photopolymerization, however, the morphology of the liquid crystalline domains became crylindric and the axial direction of the cylindric domain was at an angle of about 45° to the layers of the ordered molecular chains. The polymerization initiated by azobisisobutyronitrile (AIBN) resulted in the phase separation. The morphology of the liquid crystalline domains was maintained although the cholesteric structure of the composite was partly destroyed. © 1993 John Wiley & Sons, Inc.