Abstract— Photoinduced changes that were revealed for ferroelectric liquid‐crystalline systems with helical supra‐molecular structures induced with chiral α,β‐unsaturated ketones have been summarized. Photoinduced inversion of the spontaneous polarization sign and a concomitant increase in its absolute value and other ferroelectric parameters were observed. The E‐Z photoisomerization of the chiral compounds was determined to be responsible for the discovered effects.