3D ordered macroporous (3DOM) TiO2 was synthesized by the method of colloidal crystal template (CCT) using tetrabutyl titanate as precursor solution, and the photocatalysts of the 3DOM TiO2-supported CeO2 nanolayer with different weight ratios of CeO2 to TiO2 were successfully prepared by the gas bubbling-assisted membrane precipitation (GBMP) method. The catalysts were systematically characterized by means of scanning electron microscopy (SEM), transmission electron microscopy (TEM), mercury intrusion porosimetry (MIP), X-ray photoelectron spectroscopy (XPS), UVvis diffuse reflectance spectroscopy (DRS), and photoluminescence spectra (PL). The slow light effect of photonic crystal (3DOM structure) can enhance absorption efficiency of solar irradiation. Moreover, the introduction of CeO2 nanolayers can effectively extend the photoresponse from UV to visible region and improve the separation of photogenerated electronhole pairs. The photocatalytic activities for the reduction of CO2 with H2O were evaluated by the production of main product (CO). 3DOM CeO2/TiO2 photocatalysts exhibit high catalytic activity for the photocatalytic reduction of CO2 with H2O under simulated solar irradiation.