In this work, a series of MnxCd1-xS solid solutions as efficient photocatalysts for hydrogen evolution with visible light response were synthesized via a co-precipitation method firstly. Then, the hierarchical Bi2MoO6/Mn0.2Cd0.8S heterostructured composite was prepared by combining Mn0.2Cd0.8S composite with Bi2MoO6 nanocrystalline through a hydrothermal process. The optimized Mn0.2Cd0.8S composite's photocatalytic activity is more than 3 times of pristine CdS and the prepared Bi2MoO6/Mn0.2Cd0.8S nanocomposites exhibited a significantly improved photocatalytic activity for hydrogen evolution from water with visible light response comparing with single Mn0.2Cd0.8S composite. The optimized photocatalytic activity of Bi2MoO6/Mn0.2Cd0.8S composite is around 10 times of pristine CdS. The excellent photocatalytic activity of Bi2MoO6/Mn0.2Cd0.8S composite might be ascribed to the well-matched energy band structures of the Bi2MoO6 and Mn0.2Cd0.8S. Furthermore, the heterojunctions in Bi2MoO6/Mn0.2Cd0.8S composite might also do some contributions to improve its photocatalytic activities to some extent. A possible photocatalytic mechanism was proposed. Due to its excellent photocatalytic activity and good stability for hydrogen evolution from water, the obtained hierarchical Bi2MoO6/Mn0.2Cd0.8S composite has potential application in photocatalytic hydrogen evolution from water by using solar power. (C) 2019 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.