New class of photo and electrically switchable azobenzene containing pendant bent-core liquid crystalline monomers (AZBM 1, 2, and 3) and their polymers (AZBP 1, 2, and 3) are reported. The synthesized precursors, monomers, and polymers were characterized by FT-IR, H-1, and C-13 NMR spectroscopy. Thermal stability of polymers was examined by thermogravimetric analysis and revealed stable up to 260 degrees C. The mesophase transition of monomers and polymers are observed through polarized optical microscopy (POM) and further confirmed by differential scanning calorimetry (DSC). The electrically switching property of monomers and their polymers were studied by electro-optical method. Among the three monomers AZBM 1, 2, and 3, AZBM 1 and 2 exhibit antiferroelectric (AF) switching and AZBM 3 exhibits ferroelectric (F) switching behavior. On the other hand, low molecular weight polymers (AZMP 1, 2, and 3) show weak AF and F switching behavior. The photo-switching properties of bent-core azo polymers are investigated using UV-vis spectroscopy, trans to cis isomerization occurs around 25 s for AZBP-1 and 30 s for AZBP-2 and 3 in chloroform, whereas reverse processes take place around 80 and 90 s. (C) 2012 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 936-946