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-1h-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.