This paper describes a high efficiency photoelectrochemical electrode, i.e., TiO2/CdS/ZnIn2S4 nanorod-nanosheet arrays (NRSs) for photoelectrochemical water splitting. On the basis of optimal quantity of ZnIn2S4 nanosheets and optimal thickness of CdS buffer layer, the as-prepared TiO2/CdS/ZnIn2S4 NRSs exhibit a higher photoelectrochemical performance, the photocurrent density reaches 9.33 mA cm−2 at 0.53 V versus Ag/AgCl. The superior performance observed over this TiO2/CdS/ZnIn2S4 NRSs can be ascribed to a higher efficiency of light-harvesting ability, ideal energy band alignment, accelerated charge transmission and increased chemical stability. This study opens up a new available way to design and construct photoelectrodes for photoelectrochemical water splitting and other solar conversion materials.