The　application　of　supermolecular　naonostructures　in　the　photocatalytic　carbon　dioxide　reduction　reaction　(CO2RR)　has　attracted　increasing　attentions.　However,　it　still　faces　significant　challenges,　such　as　low　selectivity　for　multi-electron　products　and　poor　stability.　Here,　the　cuprous　oxide　(Cu2O)-modified　zinc　tetraphenylporphyrin　ultrathin　nanosheets　(ZnTPP　NSs)　are　successfully　constructed　through　the　aqueous　chemical　reaction.　Comprehensive　characterizations　confirm　the　formation　of　type-II　heterojunction　between　Cu2O　and　ZnTPP　in　Cu2O@ZnTPP,　and　the　electron　transfer　from　Cu2O　to　ZnTPP　through　the　Zn-O-Cu　bond　under　the　static　contact.　Under　the　visible-light　irradiation　(λ　＞　420　nm),　the　optimized　Cu2O@ZnTPP　sample　as　catalyst　for　photocatalytic　CO2RR　exhibits　the　methane　(CH4)　evolution　rate　of　120.9　μmol/g/h,　which　is　∼　4　and　∼　10　times　those　of　individual　ZnTPP　NSs　(28.0　μmol/g/h)　and　Cu2O　(12.8　μmol/g/h),　respectively.　Meanwhile,　the　CH4　selectivity　of　∼　98.7　%　and　excellent　stability　can　be　achieved.　Further　experiments　reveal　that　Cu2O@ZnTPP　has　higher　photocatalytic　conversion　efficiency　than　Cu2O　and　ZnTPP　NSs,　and　the　photoinduced　electron　transfer　from　ZnTPP　to　Cu2O　can　be　identified　via　the　path　of　ZnTPP→　(ZnTPP•ZnTPP)*→　ZnTPP-→　Zn-O-Cu　→　Cu2O.　Consequently,　Cu2O@ZnTPP　exhibits　a　shorter　electron-hole　separation　lifetime　(3.3　vs.　9.3　ps)　and　a　longer　recombination　lifetime　(23.1　vs.　13.4　ps)　than　individual　ZnTPP　NSs.　This　work　provides　a　strategy　to　construct　the　organic　nanostructures　for　photocatalytic　CO2RR　to　multi-electron　products.　©　2024　Elsevier　Inc.