A novel principle for photochemical control of optical properties of ferroelectric liquid crystal (FLC) is presented, which is based on photochemically induced switching of polarization of FLC triggered by photoisomerization of azobenzene derivatives doped in FLC. At the irradiated sites of the azobenzene/FLC mixtures, flip of polarization was induced, causing the change of the optical properties. The process was found to be fast, reversible, and repeatable.