Artificial photocatalysis provides a promising approach for CH₄ selective conversion into CH₃OH under mild reaction conditions. However, the over-oxidization by the active oxygen radical species impedes for the high efficiency of photocatalytic conversion of CH₄ to CH₃OH. Here, we proposed a strategy of the transfer of key intermediates •CH₃ from host photocatalyst surface for stability to improve CH₄ conversion to CH₃OH products. A Co₃O₄/ZnO composited photocatalyst was designed to efficiently convert CH₄ to CH₃OH with a rate of 366 μmol g^-1h⁻¹ under simulated sunlight irradiation, while the parent ZnO only completely overoxidized CH₄ into CO₂. We uncovered that Co₃O₄ played a new role as the active site for the adsorption of •CH₃ key intermediates and the desorption of CH₃OH to suppress CH₄ overoxidation on ZnO surface. This work highlights cocatalyst for •CH₃ intermediate stabilization to control the pathway of photocatalytic selective oxidation of CH₄ into CH₃OH.