In order to increase the transport channels of the photogenerated electrons and enhance the photosensitizer loading ability of the electrode, a new TiO₂-ZnO nanorod hierarchical structure is prepared through two-step hydrothermal process. First, TiO₂ nanorod array is grown on the FTO conductive glass substrate by hydrothermal proess. Then, ZnO sol is coated onto the TiO₂ nanorods through dip-coating method and inverted to ZnO seed layer by sintering. Finally, the secondary ZnO nanorods are grown onto the TiO₂ nanorods by the sencond hydrothermal method to form the designed TiO₂-ZnO nanorod hierarchical structure. A spin-coating assisted successive ionic layer reaction method (SC-SILR) is used to deposit the CdS nanocrystals into the TiO₂ nanorod array and the TiO₂-ZnO nanorod hierarchical structure is used to form the CdS/TiO₂ and CdS/TiO₂-ZnO nanocomposite films. Different methods, such as SEM, TEM, XRD, UV-Vis and transient photocurrent, are employed to characterize and measure the morphologies, structures, light absorption and photoelectric conversion performance of all the samples, respectively. The results indicate that, compared with the pure TiO₂ nanorod array, the TiO₂-ZnO nanorod hierarchical structure can load more CdS photosensitizer. The light absorption properties and transient photocurrent performance of the CdS/TiO₂-ZnO nanorod hierarchical structure composite film are evidently superior to that of the CdS/TiO₂ nanocomposite films. The excellent photoelctrochemical performance of theTiO₂-ZnO hierarchical structure reveales its application prospect in photoanode material of the solar cells.