Fully utilizing solar energy for catalysis requires integration of conversion mechanisms and therefore delicate design of catalyst structures and active species. Here, a MOF crystal engineering method was developed to controllably synthesize the copper-ceria catalyst with well-dispersed photoactive Cu-[O]-Ce species. Using preferential CO oxidation as a model reaction, the catalyst showed remarkably efficient and stable photoactivated catalysis, which found practical application in feed gas treatment for fuel cell gas supply. The coexistence of photochemistry and thermochemistry effects contributes to the high efficiency. Our results demonstrate a catalyst design approach with atomic or molecular precision and the combinatorial photoactivation strategy for solar energy conversion.