We report on a series of three bent-core liquid crystals containing tetrathiafulvalene units. Their characterization consisted of electro-optical observations, second-harmonic generation (SHG) analysis, and x-ray diffraction measurements. Compound I exhibits a lamellar optically isotropic phase on cooling from the isotropic liquid and undergoes a nonreversible field-induced transition to a birefringent state. The two others present two-dimensional structural periodicities, being only compound II switchable. Additionally, the electron density maps of compounds II and III have been obtained based on the analysis of the x-ray diffraction intensities. According to SHG measurements the ground state is antiferroelectric in the three compounds. A quite good SHG performance is found in compounds I and II.