Direct oxidation of methane to methanol utilizing molecular oxygen under mild conditions is an important yet challenging process due to the difficulty in activating of methane under such conditions. In this research, we report on zeolitic octahedral metal oxides based on cobalt vanadotungstates, which act as the catalysts for the oxidation of methane using molecular oxygen as the oxidant without co-reductants at a low temperature of 90 °C even as low as 60 °C. This catalytic process results in the high-yield production of methanol as the primary product. The micropores within the catalyst are critical for achieving high activity in the reaction, in which molecular oxygen is activated. The active species in the reaction are found to be hydroxyl-based. Both VO