So herein, for the first time, we found that the catalytic amount of K2CO3 could act as a highly efficient catalyst in the selective oxidation of DHFM to BHMF by using H2O in an open-air system, which has not been reported so far. We have confirmed that both the base and air are necessary for the oxidation of α-hydroxy ketone based on lots of control experiments. We also studied the factors of solvent, water capture additives, amount of base, reaction temperature, and reaction time systematically which affect the oxidation of Benzoin and DHMF. Satisfied, for the first time, the benzoin could be converted to the corresponding benzil in 94.9% yield with a catalytic amount of 10% K2CO3 after 5 hours in DMSO under an open-air system with the additive AC. The additives MS 4Å, AC, and MnO2 had a significant effect on the oxidation of benzoin, which could be due to their properties in trapping the byproduct H2O and promoting the equilibrium of the reaction. With using additives MS 4Å, AC, and MnO2, the benzil yield increased from 84.3%, 86.4%, and 72.9% at the beginning of the reaction to 94.6%, 99.0%, and 99.0% respectively after 7 hours. Solvent had a great effect on the reactivity and efficiency of the catalytic oxidation of benzoin. The protic polar solvent t-BuOH showed the best result with a 96.9% yield of benzil even on a large scale under mild reaction conditions of 20% of K2CO3, AC 200 mg, 80 °C, 7 h, open air system.