Electrodeposition was used to fill the voids of PS colloidal crystals on silicon wafer with Ni and Ni inverse opal was obtained. The influence of chemical etching of silicon wafer on the electrodeposition of Ni was studied by using cyclic voltammetry scan. The resulted Ni inverse opal was characterized by scanning electron microscopy and X-ray diffraction. It showed that chemical etching of silicon surface is beneficial for the deposition of Ni on silicon wafer. Ni grown in the voids of PS colloidal crystals is the polycrystalline phase and the ordered porous structure of Ni is formed after the removing of the PS template.