Two novel homochiral enantiomers, trinuclear ionic clusters [(NiL1)(2)-Na]+NCS- center dot MeOH center dot Et2O (1) and [(NiL2)(2)Na]+NCS- center dot MeOH center dot Et2O (2) [H2L1 = N,N-bis(3-methoxysalicylidene)-(1R,2R)-1,2-diphenylenediamine; H2L2 = N,N-bis(3-methoxysalicylidene)-(1S,2S)-1,2-diphenylenediamine], have been synthesized and structurally characterized. Both complexes have C-2 symmetry and crystallize in space group P2(1). Ferroelectric measurements reveal that complexes 1 and 2 represent a new type of ionic ferroelectric based on metal-organic coordination with a polarization value higher than that of KH2PO4.