The synthesis of several symmetrical bent-core compounds with two or four fluorine atoms as substituents on the calamitic units is reported. The influence of fluorine substitution concerning its effect upon the mesophase structure and switching behavior was investigated. The synthesized compounds are built from resorcinol as central core and contain seven phenyl rings linked by ester, imine and azo units with terminal decyloxy/dodecyloxy chains. The mesophases were characterized by polarizing optical microscopy, differential scanning calorimetry, electro-optical investigations and X-ray diffraction (XRD) studies. The photochemical characterisation of bent-core azobenzene compounds confirmed the structure of E isomer. The temperature range of mesophases increases upon the introduction of fluorine substituents, as compared with the corresponding unsubstituted compound. All the compounds exhibit antiferroelectric properties. Depending on the number of the F substituents, racemic SmCSPA mixtures and SmCAPA homochiral structures were identified. High values of spontaneous polarization up to 900 nC/cm2 were recorded. DFT studies were used to calculate the minimum energy molecular structures, the dipole moments and the electrostatic potential surfaces of the compounds.