Methane photooxidation into methanol offers a promising approach for producing high-value chemicals and efficiently storing solar energy. However, the ease with which C–H bonds in methanol products break leads to continuous dehydrogenation and methanol peroxidation, posing a major challenge in direct methane-to-methanol conversion. This review summarizes the mechanisms and strategies for inhibiting methanol peroxidation in methane photooxidation, focusing on radical and active site mechanisms. Radical mechanisms involve controlling active radicals like hydroxyl (·OH) and hydroperoxyl (·OOH) to prevent peroxidation. Active site mechanisms aim to promote methanol desorption or regeneration, reducing its reactivity. Strategies include optimizing the concentration of ·OH, using cocatalysts to suppress ·OH formation, and modifying active sites to enhance desorption or regeneration of methanol. The review also highlights the importance of developing advanced characterization techniques and designing efficient photocatalysts to achieve high selectivity and low peroxidation. Future research should focus on improving charge transfer dynamics, optimizing catalysts for ideal ·OOH generation, and integrating multifunctional active sites to address the challenges of methanol peroxidation in methane photooxidation.Methane photooxidation into methanol offers a promising approach for producing high-value chemicals and efficiently storing solar energy. However, the ease with which C–H bonds in methanol products break leads to continuous dehydrogenation and methanol peroxidation, posing a major challenge in direct methane-to-methanol conversion. This review summarizes the mechanisms and strategies for inhibiting methanol peroxidation in methane photooxidation, focusing on radical and active site mechanisms. Radical mechanisms involve controlling active radicals like hydroxyl (·OH) and hydroperoxyl (·OOH) to prevent peroxidation. Active site mechanisms aim to promote methanol desorption or regeneration, reducing its reactivity. Strategies include optimizing the concentration of ·OH, using cocatalysts to suppress ·OH formation, and modifying active sites to enhance desorption or regeneration of methanol. The review also highlights the importance of developing advanced characterization techniques and designing efficient photocatalysts to achieve high selectivity and low peroxidation. Future research should focus on improving charge transfer dynamics, optimizing catalysts for ideal ·OOH generation, and integrating multifunctional active sites to address the challenges of methanol peroxidation in methane photooxidation.