Photocatalytic hydrogen production using water splitting is of potential importance from the viewpoint of renewable energy development. Herein, Bi2O3-TiO2 composite photocatalysts presented as Bi-Bi2O3-anatase-rutile TiO2 multijunction were first fabricated by a simple impregnation-calcination method using Bi2O3 as H-2-production cocatalysts. The obtained multijunction samples exhibit an obvious enhancement in photocatalytic H-2 evolution activity in the presence of glycerol. The effect of Bi2O3 amount on H-2-evolution activity of TiO2 was investigated and the optimal Bi2O3 content was found to be 0.89 mol%, achieving a H-2-production rate of 920 p.mol h(-1), exceeding that of pure TiO2 by more than 73 times. The enhanced mechanism of photocatalytic H-2 -evolution activity is proposed. This study will provide new insight into the design and fabrication of TiO2-based hydrogen-production photocatalysts using low-cost Bi2O3 as cocatalyst. (C) 2016 Elsevier B.V. All rights reserved.