Partial　oxidation　of　methane　(CH4)　to　value-added　products　is　significantly　challenging　due　to　the　highly　inert　chemical　property　of　CH4　at　ambient　conditions　and　easy　over-oxidation　into　carbon　dioxide　(CO2)　or　carbon　monoxide　(CO)　at　elevated　temperatures　and　pressures.　Targeting　this　challenge,　the　efficient　photocatalytic　coupling　of　CO2　and　CH4　into　ethanol　is　demonstrated,　using　a　cerium　(Ce)-doped　zinc　oxide　(ZnO)　photocatalyst　with　abundant　Ce─O─Zn　units.　Under　light　illumination,　CO2　is　adsorbed　on　the　Ce　atoms　and　photo-reduced　to　CO,　and　CH4　is　captured　by　the　Zn　atoms　and　photo-oxidized　to　hydroperoxymethane　(CH3OOH).　The　close　proximity　of　Ce　and　Zn　atoms　on　the　Ce─O─Zn　units　allowed　to　further　efficiently　couple　the　as-formed　CO　and　CH3OOH into　ethanol.　Without　additional　Oxygen　(O2)　oxidant　or　sacrificial　regent,　the　ethanol　production　rate　reached　580 µmol g−1 h−1,　substantially　exceeding　previously　reports　on　photocatalytic　CH4　oxidation.　This　work　features　to　convert　two　greenhouse　gases　into　value-added　chemicals　with　adjacent　and　asymmetric　reaction　sites,　suggesting　attractive　potentials　for　CH4　and　CO2　utilization.　©　2023　Wiley-VCH　GmbH.