Significant efforts have been devoted to develop efficient visible-light-driven photocatalysts for the conversion of CO2 to chemical fuels. The photocatalytic efficiency for this transformation largely depends on CO2 adsorption and diffusion. However, the CO2 adsorption on the surface of photocatalysts is generally low due to their low specific surface area and the lack of matched pores. Here we report a well-defined porous hypercrosslinked polymer-TiO2-graphene composite structure with relatively high surface area i.e., 988 m2 g-1 and CO2 uptake capacity i.e., 12.87 wt%. This composite shows high photocatalytic performance especially for CH4 production, i.e., 27.62 μmol g-1 h-1, under mild reaction conditions without the use of sacrificial reagents or precious metal co-catalysts. The enhanced CO2 reactivity can be ascribed to their improved CO2 adsorption and diffusion, visible-light absorption, and photo-generated charge separation efficiency. This strategy provides new insights into the combination of microporous organic polymers with photocatalysts for solar-to-fuel conversion.