Hydrothermal reaction of (S)-1,1'1' '-2,4,6-trimethylbenzene-1,3,5-triyl-tris(methylene)-tris-pyrrolidine-2-carboxylic acid (TBPLA) with Ni(ClO4)(2)center dot 6H(2)O gave pale green block crystals of 1. X-ray crystal structure analysis showed the complex to be a trinuclear descrete homochiral molecule with each Ni center sitting in distorted octahedron geometries. Anisotropic permittivity measurements reveal that 1 exhibits huge dielectric anisotropy along its three different crystal axes that is ca. 3.5 times of epsilon(r) (E//c)/epsilon(r) (E//b) with temperature and frequency independence.