Herein, we propose that an efficient CH4 partial photooxidation to methanol depends on appropriate band edge positions in photocatalysts. We demonstrated our hypothesis using Bi2O3 since this semiconductor has a valence band favorable to produce hydroxyl radicals (•OH) and a conduction band not advantageous to superoxide radicals (O2•-) which is crucial to keep O2 available for methyl radical (•CH3) capture and CH3OH formation. A notable and selective partial photooxidation of methane to methanol was observed under visible light at room temperature and pressure. As a result, the productivity of methanol over Bi2O3 can reach approximately 1200 μmol g-1 h-1 with c.a. 65% selectivity avoiding overoxidation to CO2. The isotope labeling experiment (13CH4) confirmed that methane acts as the carbon source of methanol and ESR measurements proved the •CH3 and •OH generation. Besides, Bi2O3 exhibited good stability after 5 cycles maintaining a high and selective methanol production. These results provide insight into critical photocatalyst properties for the partial photooxidation of methane to methanol.