In this paper, the CuInS2 films were firstly modified with CdS and CdS/ZnO/ZnO:Al/Au layers in order to improve the photoelectrochemical (PEC) water splitting efficiency. The CuInS2 photoelectrode was synthesized by electrodeposition method as a facial and green method, on the FTO substrate. The effects of pH and concentration of Na2S electrolyte solution on the photocurrent density of photoelectrode samples were studied. As a p-n junction photocathode, the CIS/CdS/ZnO/ZnO:Al/Au photoelectrode indicates the enhanced PEC activity. The photocurrent density of CIS/CdS/ZnO/ZnO:Al/Au photoelectrode reaches to 1.91 mA/cm2, while is about 2.5 times higher than that for CuInS2 film at pH = 8 (−0.6 V vs Ag/AgCl). The formation of a p-n junction at the CuInS2 photoelectrode surface not only reduces the recombination of electron-hole pairs but also increases the PEC response and water splitting performance of the as-prepared CIS/CdS/ZnO/ZnO:Al/Au photoelectrode.