The synthesis and properties of a new series of chiral fluoro-substituted benzoyloxybenzoates with nonchiral chains ranging from heptyloxy to octadecyloxy are reported. The mesomorphic properties of all of the compounds have been examined by a combination of optical polarized light microscopy, differential scanning calorimetry, and miscibility studies. They show rich polymorphism, and seven compounds exhibit the antiferroelectric (SmC*(A) ) phase. The spontaneous polarization in the ferroelectric (SmC*) phase has been measured as a function of temperature for selected compounds.