The construction of highly efficient Z-scheme photocatalytic system is regarded as a hot research topic in the fields of environmental remediation and renewable energy production. In this work, a novel Z-scheme CeO2/CeVO4/V2O5 photocatalyst is successfully prepared by using solid phase reaction method. The photocatalytic degradation of organic pollutant (Methylene Blue) with simultaneous hydrogen production is efficiently realized over the prepared Z-scheme CeO2/CeVO4/V2O5 photocatalysts under visible-light irradiation. The effects of treatment temperatures and treatment times of CeO2/V2O5 composite on the photocatalytic performance of Z-scheme CeO2/CeVO4/V2O5 photocatalyst are studied. The as-prepared Z-scheme CeO2/CeVO4/V2O5 (550-3) photocatalyst heat-treated at 550 degrees C for 3.0 h exhibits the highest photocatalytic performance. It can be ascribed to a moderate amount of CeVO4 nanoparticles generated between CeO2 and V2O5. The generated CeVO4 nanoparticles can be used as effective conductive channel to transfer the photo-generated carriers. At the same time, as redox reaction centers it can further accelerate the transfer of photo-generated electrons, effectively enhancing the separation efficiency of photo-generated electron and hole pairs. Furthermore, cyclic test demonstrates that the as-prepared Z-scheme CeO2/CeVO4/V2O5 (550-3) photocatalyst still maintains a high level of photocatalytic activity within five periods under the same conditions. Moreover, the related photocatalytic mechanism for degradation of organic pollutants with simultaneous hydrogen evolution over the Z-scheme CeO2/CeVO4/V2O5 (550-3) photocatalyst is proposed. Perhaps, this study affords a simple and novel method to design and develop next generation of highly efficient Z-scheme photocatalysts. (C) 2019 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.