The novel Z-scheme heterojunction photocatalyst W18O49/CeO2 was prepared by hydrothermal synthesis. The photocatalytic properties of W18O49/CeO2 were evaluated by photocatalytic hydrogen evolution under visible light. The result shows that the 15 wt% W18O49/CeO2 composite has the best hydrogen production efficiency of about 0.2061 mmol g(-1) h(-)(1), which was 1.93 times higher than that the obtained pure CeO2. The characterization results demonstrated that the existence of Z-scheme heterojunction structure at the contact interface of W18O49 and CeO2 was the origin of the enhanced photocatalytic performance for hydrogen evolution, which could greatly increase the accumulation of photo-generated electrons and the separation efficiency of charge carrier. In accordance with density functional theory (DFT) calculation, we further confirmed the formation of Z-scheme heterojunction structures. This work is anticipated to expand the ideas for modifying CeO2 semiconductor materials to improve the rate of photocatalytic hydrogen production. (C) 2020 Elsevier Inc. All rights reserved.