Photocatalytic　oxidative　coupling　of　methane　(POCM)　is　a　direct　way　for　the　methane　transformation　into　≥C2　alkanes.　However,　the　typical　oxygen　activation　path　often　leads　to　the　formation　of　strong　oxidizing　superoxide　radical　(O2-)　species,　which　makes　the　whole　reaction　face　serious　selectivity　problems.　Herein,　we　constructed　N　and　oxygen　vacancy　dual　active　sites　on　TiO2{001}　nanosheets　(TiO2-NVo)　to　regulate　the　oxygen　activation　pathway　and　achieve　a　high　activity　and　selectivity　of　photocatalytic　OCM.　Compared　with　ordinary　Au/TiO2{001}　nanosheets,　the　alkane　yields　of　Au/TiO2-NVo　are　increased　from　16　μmol　h-1　to　32　μmol　h-1,　and　the　selectivity　of　alkanes　increased　from　61%　to　93%.　The　performance　is　superior　when　compared　with　the　reported　till　date　in　photocatalytic　OCM　in　batch　reactors.　The　superior　performance　originates　from　the　unique　N-Vo　dual　active　sites　for　synergistically　cleaving　the　detrimental　O2-　into　desirable　mono-oxygen　active　species　(O·-)　to　suppress　undesired　overoxidation　reaction.　The　formed　O·-　species　from　O2-　dissociation,　in　turn,　is　active　for　the　selective　H　abstraction　of　CH4　into　•CH3　to　improve　the　subsequent　C-C　coupling　reaction　on　the　Au　nanocluster　surface.　This　work　provides　a　new　approach　of　O2　dissociation　to　address　the　overoxidation　of　methane　in　an　aerobic　environment　for　achieving　highly　selective　CH4　conversion.　©　2024　American　Chemical　Society.