A maleonithiledithiolene nickel(Ⅲ) ionic pair complex containing substituted benzylpyridinium,[CNBz-2-MePy][Ni(mnt)2]([CNBz-2-MePy]+ is 1-(4′-cyanobenzyl)-2-methylpyridinium,mnt2-is maleonitriledithiolate),was prepared and characterized by elemental analyses,IR and single crystal X-ray diffraction.The complex consists of a [CNBz-2-MePy]+ cation and a [Ni(mnt)2]2-anion.The anions and cations stack into columns along a axis in the solid state respectively,and the Ni(Ⅲ) ions in the anions form a 1D alternating chain by Ni…Ni,Ni…S,and π-π stacking interactions.Magnetic susceptibility measurements in the temperature range 75-300 K show that [CNBz-2-MePy][Ni(mnt)2]exhibits antiferromagnetic behavior.