Photocatalytic　methane　conversion　into　liquid　oxygenates　using　O-2　oxidants　provides　a　promising　approach　for　high-value　chemicals.　The　generation　of　reactive　oxygen　species　and　their　reaction　pathway　are　key　to　determine　the　oxygenate　selectivity.　Here,　an　interstitial　Zn-i　defect　ZnO　(ZnO(Zn-i))　is　developed　through　thermal　decomposition　of　the　ZnO2　precursor.　Zn-i　favors　the　O-2　adsorption　at　a　terminal　adsorption　configuration　and　induces　effectively　the　conversion　O-2　into　the　desired　center　dot　OOH　instead　of　center　dot　OH　for　improving　the　yield　and　selectivity　of　oxygenates.　For　comparison,　O-2　adsorbed　in　a　lateral　configuration　tends　to　be　converted　into　excessive　center　dot　OH　on　the　typical　Au/ZnO.　As　a　result,　ZnO(Zn-i)　shows　the　liquid　oxygenates　yield　of　6080　mu　mol　g(-1)　with　98.6%　selectivity,　which　leads　to　10　times　lower　than　Au/ZnO　for　CO2　release　of　overoxidation.　This　work　provides　a　pathway　for　O-2　adsorption　and　activation　to　regulate　the　photocatalytic　CH4　oxidation　conversion　into　liquid　oxygenates.