Two novel homochiral enantiomers, trinuclear ionic clusters [(NiL(1))(2)Na](+)NCS(-).MeOH.Et(2)O (1) and [(NiL(2))(2)Na](+)NCS(-).MeOH.Et(2)O (2) [H(2)L(1) = N,N'-bis(3-methoxysalicylidene)-(1R,2R)-1,2-diphenylenediamine; H(2)L(2) = 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 KH(2)PO(4).