Nickel-bisdithiolate complexes with a ferrocene-containing 2nd order nonlinear optical chromophore as a cation, (FcCH=CHPyMe)[NiL2] where L = dmit (1a), dddt (1b) and debt (1c) were synthesized by the cation exchange reaction. In the X-ray crystal structure of complex (1a), no intrastack but interstack S...S interactions less than 3.7 Angstrom are observed. This complex was revealed to be an insulator at room temperature. However, (FcCH=CHPyMe)(x)[Ni(dMit)(2)] (0 < x < 1) (3) needle grown in an H-type electrochemical cell shows semiconductor behavior (E-a = 106 meV) over the temperature range measured (30 similar to 300 K) with sigma(RT) = 1 Omega(-1)cm(-1). The electronic transition at UV-vis-NIR region was measured for the nickel complexes and discussed.