Photosensitive liquid crystals represent an important class of functional materials that experience rapid development. Hereby, we present novel bent-core liquid crystals bearing a lateral substitution on the central core and in the vicinity of the photosensitive unit—an azo group. The azo group enables fast (E)-to-(Z)-isomerization upon irradiation with UV-light and visible light, while the substitution facilitates the high stability of the photochemically formed (Z)-isomer. The effectiveness of the irradiation and the composition of photostationary states was determined by UV/Vis and 1H NMR spectroscopy. A nematic phase formed by the materials was characterized by differential scanning calorimetry and optical polarizing microscopy. We show that the materials easily change their relative configuration of the N=N double bond not only in solution, but also in the mesophase, which leads to fast isothermal phase transition from the nematic phase to isotropic liquid.