The　photocatalytic　non-oxidative　coupling　of　methane　(NOCM)　process　is　a　desirable　reaction　that　uses　solar　energy　to　convert　methane　into　an　equal　proportion　of　ethane　and　hydrogen.　However,　most　current　photocatalysts　suffer　from　low　product　yields　and　selectivity　due　to　the　over-oxidation　of　methane　or　catalyst　deactivation　by　coke　deposition.　In　this　study,　a　Ag/In2O3　photocatalyst　was　synthesized　by　a　simple　deposition　precipitation　method　for　the　non-oxidative　coupling　of　methane　in　a　batch　reactor　under　photoirradiation　at　room　temperature　and　atmospheric　pressure.　Ethane　yields　of　up　to　450.26　μmol　g−1　h−1　with　a　high　selectivity　of　88%　were　achieved.　The　characterization　results　showed　that　Ag+　species　were　stably　loaded　in　oxygen　vacancies　on　the　In2O3　carrier.　The　Ag+　accepted　the　photogenerated　electrons　from　In2O3,　which　inhibited　the　recombination　of　the　electrons　and　photogenerated　holes,　while　the　methane　was　oxidized　by　the　holes　to　ethane.　This　study　offers　a　new　insight　into　the　design　of　photocatalytic　NOCM　reactions.　©　2023　The　Royal　Society　of　Chemistry.