Using polystyrene spheres and EO20PO70EO20 as double templates, a three-dimensionally ordered macroporous (3DOM) CeO2-ZrO2 material was synthesized by the sol-gel method combined with the decompression filling method. The composition, structure, morphology, and surface physicochemical properties of the material were characterized by XRD, XPS, UV-vis/DRS, SEM, TEM, HR-TEM, and N-2 adsorption-desorption measurements. The results show that the material has a good crystal structure with neat and ordered macroporous multilayered, open, and transparent structure and a clear shape of the dendritic crosslinking. Moreover, the walls of the material are formed by accumulating smaller particles, thus improving the light absorption efficiency. The unique morphology of 3DOM CeO2-ZrO2 significantly increased its activity during the multimode photocatalytic experiments. In the photocatalytic hydrogen evolution experiment, 3DOM CeO2-ZrO2 showed a stronger ability of water splitting into hydrogen. This indicates the dendritic crosslinked 3DOM CeO2-ZrO2 can simultaneously enhance the photodegradation and photolysis of water. (C) 2017 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.