The occurrence of antiferroelectric phenomenon in achiral composites composed of azo-benzene containing liquid crystals was observed. Some of the composites evidenced typical antiferroelectric polarization hysteresis loop in the mesophase, showing bilayer smectic C-2 mesophases with some interdigitation grade at the layer interface in a broad temperature range. Surprisingly composites of similar structure developed pyroelectricity but not switchable states. This new class of antiferroelectric materials is also capable of producing E-Z photoisomerization making them good candidates for energy harvesting. (C) 2011 Elsevier B. V. All rights reserved.