Overall, we establish a very convenient visible-light driven aerobic oxidation of methane with HTFA to MTFA at room temperature, involving the gas-phase oxidative reactions of CH4/O2 with NOCl to give CH3O-NO2/HCl selectively and the liquid-phase transform reactions of CH3O-NO2/HCl with HTFA to form MTFA and NOCl effectively. This is a novel two-phase methane conversion without any special catalysts or reagents. MTFA could be obtained in a high yield (over 80%) based on CH4 in both batch and continuous experiments. Especially, in the continuous reactions under ambient conditions, MTFA could be produced smoothly and its selectivity is over 90% in 7 days. The ratio of initial and input CH4/O2 is 2:1 in these reactions, which is not only consistent with the aerobic oxidation of methane to methanol but also beyond the explosion limit of methane. MTFA is more easily hydrolyzed to afford methanol at room temperature. It is feasible to be a practical and commercial process in industry after further exploration and improvement.