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 Å 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 (Ea =106 meV) over the temperature range measured (30 ∼300 K) with σRT = 1 Ω-1cm-1. The electronic transition at UV-vis-NIR region was measured for the nickel complexes and discussed.