In this study, we report a simple, effective and universal approach to fabricate homojunction structural TiO2 nanorod array photoelectrodes through doping of gradient distributed oxygen vacancies introduced by annealing in high vacuum with controlled time. The homogeneous junction structure promotes the separation and transport of photoexcited charge carriers, and the photocurrent density of TiO2 nanorod arrays annealed in high vacuum for 2 h was 20 times higher than that of the pristine TiO2 nanorod arrays. The results indicate that annealing in high vacuum with controlled time could form a homojunction structure, which is an effective approach for further enhancing the performance of U-V visible light driven photocatalytic materials for water splitting. (C) 2017 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.