Monodisperse ZnO particles with adjustable size have been produced on a large scale by two-step seeding-growth polyol reactions. Through spin coating of supersaturated ZnO/diethylene glycol solution and evaporation of solvent, opaline ZnO photonic crystal (PC) film with good crystallinity and uniform photonic structures can be prepared from these ZnO particles. Compared with a disorderly stacked ZnO film, the ZnO PC film shows a higher activity in photocatalytic reduction of CO2 due to the generated slow photons at the edge of the photonic band gap and their promotion to the light absorption. When the electronic band gap of ZnO matches the red edge of the photonic band gap of ZnO PC, the enhancement factor of photocatalytic activity represented by CO evolution can be maximized to 2.64-fold in the current experiment. Compared to the traditional inverse opal photocatalysts, the opaline ZnO photocatalysts are prepared by simplified and scalable procedures, and they still possess the same enhancement without the photonic structure, which might be broadly used in solar energy utilization, environment protection, other green chemical processes in the future. in activity compared to ZnO and many other green chemical processes in the future.