In the present work, synthesis of a new photosensitive bent-core monomer and corresponding side-chain polymethacrylate is described. The liquid crystalline (LC) properties were studied by texture observation, calorimetric and electro-optical measurements. Structural parameters of the LC phases were established from X-ray diffraction. Due to presence of the azobenzene group both compounds revealed photosensitivity and UV-irradiation effectively induces the E–Z isomerization process. The photo-optical properties of the spin-coated films of polymethacrylate are analysed and it is found that irradiation with polarized light aligns chromophores in the direction perpendicular to the polarization plane of incident light. Photoorientation proceeds more effectively in the amorphousized films in comparison with annealed LC films.