Abstract: The synthesis of high-value-added oxygenated chemicals (such as formaldehyde, methyl formate, dimethoxymethane, polymethoxy dimethyl ether, etc.) from methanol/dimethyl ether through an oxidative route boasts advantages of high atom utilization efficiency, distinctive product characteristics, and low carbon emissions, attracting significant attention as a pathway for high-value utilization. However, the oxidation conversion of methanol/dimethyl ether also confronts several challenges, including difficulty in activating C−H bonds at low temperatures, susceptibility to deep oxidation at high temperatures, and difficulty in controlling the chain growth of C−O bonds in larger molecular products. This review will focus on the latest progress in elucidating the mechanisms of the activation and cleavage of C−H bonds in methanol/dimethyl ether molecules at low temperatures and the controllable chain growth of longer C−O bonds by relevant research teams. It aims to outline several representative catalytic reaction mechanisms, thereby providing valuable insights for this field and related research endeavors.