The review discusses the challenges and strategies involved in inhibiting methanol peroxidation during the photooxidation of methane to methanol. Methane photooxidation is a promising method for generating high-value chemicals and storing solar energy, but the propensity of C–H bonds in methanol to cleave more easily than those in methane leads to continuous dehydrogenation and methanol peroxidation. The review categorizes the mechanisms into radical and active site mechanisms and explores regulatory methods to prevent methanol peroxidation. Radical mechanisms involve controlling hydroxyl (-OH) and hydroperoxyl (-OOH) radicals, while active site mechanisms focus on methanol desorption and regeneration. The review highlights the importance of precise control over radical generation, active site reconstruction, and the design of photocatalysts to enhance methanol selectivity. Future research directions include developing advanced characterization techniques, optimizing photocatalyst design, and improving reaction system design to overcome current challenges.The review discusses the challenges and strategies involved in inhibiting methanol peroxidation during the photooxidation of methane to methanol. Methane photooxidation is a promising method for generating high-value chemicals and storing solar energy, but the propensity of C–H bonds in methanol to cleave more easily than those in methane leads to continuous dehydrogenation and methanol peroxidation. The review categorizes the mechanisms into radical and active site mechanisms and explores regulatory methods to prevent methanol peroxidation. Radical mechanisms involve controlling hydroxyl (-OH) and hydroperoxyl (-OOH) radicals, while active site mechanisms focus on methanol desorption and regeneration. The review highlights the importance of precise control over radical generation, active site reconstruction, and the design of photocatalysts to enhance methanol selectivity. Future research directions include developing advanced characterization techniques, optimizing photocatalyst design, and improving reaction system design to overcome current challenges.