A　photothermal　catalytic　system　comprising　Cu/CeO2　was　applied　to　the　reaction　between　NO,　CO　and　H2O　for　the　production　of　NH3　under　visible-light　irradiation.　High　NO　conversion　(94.4%)　and　NH3　selectivity　(66.5%)　were　achieved　over　Cu/CeO2　in　the　presence　of　H2O　at　210　°C.　Visible　light　further　improved　the　conversion　of　NO　(97.7%)　and　selectivity　for　NH3　(69.1%).　The　quasi-situ　EPR　and　in-situ　DRIFTS　results　indicated　that　CO　initially　reacts　with　H2O　to　form　an　HCO3*　intermediate,　which　then　decomposes　into　CO2　and　activated　H*.　Finally,　NO　reacts　with　activated　H*　to　produce　NH3.　The　localized　surface　plasmon　resonance　effect　of　Cu　nanoparticles　induced　by　visible　light　promotes　the　decomposition　of　HCO3*　to　CO2　and　H*,　while　regenerating　oxygen　vacancies　(OVs,　H2O　activation　sites)　at　the　CeO2　sites,　resulting　in　enhanced　NH3　production.　This　study　offers　a　convenient　approach　for　NH3　production　under　mild　conditions.　©　2023　Dalian　Institute　of　Chemical　Physics,　the　Chinese　Academy　of　Sciences