A　facile　procedure　for　doping　copper　species　into　CeO2　lattices　to　prevent　ceria　from　being　deactivated　and　to　offer　additional　active　sites　for　selective　H2S　oxidation　is　reported　here.　Among　the　prepared　catalysts,　porous　10Cu/Ce　nanorods　with　well-defined　(100)　and　(110)　reactive　planes　display　excellent　catalytic　performance,　exhibiting　H2S　conversion　and　sulfur　selectivity　of　100%　at　220　°C,　which　is　higher　than　those　of　most　reported　Ce-based　catalysts.　More　importantly,　electron　transfer　from　Cu+　to　Ce4+　suppresses　the　transfer　of　electrons　from　SO2　to　Ce4+,　leading　to　inhibition　of　SO2　oxidation　to　surface　sulfate,　which　could　deactivate　the　catalyst.　Overall,　the　results　of　systematic　experimental　and　theoretical　studies　prove　that　copper　doping　effectively　promotes　the　formation　of　oxygen　vacancies　and　resistance　against　SO2　poisoning.　Furthermore,　through　in　situ　diffuse　reflection　infrared　Fourier　transform　spectroscopy　investigation　and　density　functional　theory　calculations,　the　reaction　intermediates　in　selective　H2S　oxidation　and　mechanism　of　SO2　resistance　over　the　Cu-doped　CeO2　catalysts　are　revealed.　©　2020　Elsevier　Inc.