The introduction of surface disorders (Ti3+ or oxygen vacancies) is reported to be an effective way to improve the photoelectrochemical property of TiO2 nanomaterials. Herein, we demonstrate for the first time that the surface disorders of TiO2 nanorods can be effectively achieved by introducing Au nanoparticles on the surface of TiO2 (Au/TiO2). The XPS and EPR results display the existence of Ti3+ and oxygen vacancies in the hydrogenated Au/TiO2 nanorods. Moreover, this is the first experimental demonstration that hydrogenation of Au/TiO2 outperforms saturation photocurrent of the total of hydrogenated TiO2 and Au/TiO2 for photoelectrochemical water splitting. Such significant performance enhancement can be attributed to the strong effort between the Au and the hydrogen molecular, which would enhance the effective generation of the surface disorders.