Uniform core/shell nanostructure of ZnO/CuInS2 nanorods was synthesized using ZnO nanorod arrays as reactive templates via solution reaction. The N3 dye was sequentially assembled on the ZnO/CuInS2 arrays to construct a cascading co-sensitized nanomaterial as photoanode of solar cell. Formation process of CuInS2/ZnO nanostructure and the mechanism of CuInS2 and N3 co-sensitization were discussed. The I-V characteristic measurement indicates an enhanced efficiency by 24.8% as compared to single sensitized by N3 due to abundant light harvesting, higher chemical instability of ZnO/CuInS2 in acid dye, fast injection and transmission velocity, and the slow-down recombination of photo-excited electrons, simultaneously.