Mesoporous Co/KIT-6 and Co/SiO2 catalysts were prepared via hydrogen reduction and were subsequently used in CO2 catalytic hydrogenation to produce methane. The properties of the prepared Co/KIT-6 catalyst were investigated by low-angle X-ray diffraction, Brunauer-Emmett-Teller analysis, and transmission electron microscopy. The results indicate that the synthesized Co/KIT-6 catalyst has mesoporous structures with well-dispersed Co species, as well as higher CO2 catalytic hydrogenation activities than that of the Co/SiO2 catalyst. The Co/KIT-6 catalyst has a large specific surface area (368.9 m2 · g−1) and a highly ordered bicontinuous mesoporous structure. This catalyst exhibits excellent CO2 catalytic hydrogenation activity and methane product selectivity; the CO2 conversion and methane selectivity of the Co/KIT-6 catalyst at 280°C are 48.9% and 100%, respectively. The highly ordered, bicontinuous mesoporous structure of the Co/KIT-6 catalyst improves selectivity for the methane product.