Poly(p-phenylenevinylene) (PPV) derivatives with ferroelectric liquid crystallinity were synthesized by substituting fluorine-containing chiral liquid crystalline (LQ groups into the side chains, The di-substituted monomer showed various LC phases such as chiral nematic (N*), twist grain boundary A (TGBA), and chiral smectic C (S-C*) phases, The PPV polymers showed a stable enantiotropic S-C* phase characteristic of ferroelectricity, as well as a fluorescence.