CeO2-based　catalysts　are　potentially　suitable　for　H2S-selective　oxidation,　but　their　practical　application　is　limited　due　to　the　problem　of　sulfate　formation.　Herein,　we　report　a　facile　citric　acid-assisted　hydrothermal　process　for　the　fabrication　of　porous　Fe-doped　CeO2　with　flower-like　morphology　that　can　drastically　promote　the　catalytic　activities　of　CeO2　with　high　durability.　Among　the　synthesized　catalysts,　the　one　with　well-defined　(110)　and　(100)　planes　is　highly　active　for　H2S-selective　oxidation　with　H2S　conversion　and　sulfur　selectivity　of　almost　100%　at　220　°C,　superior　to　most　of　the　reported　Ce-based　catalysts.　Meanwhile,　outstanding　catalytic　stability　is　achieved　because　the　presence　of　Fe　ions　alleviates　ceria　deactivation　due　to　sulfation.　The　results　of　systematic　investigation　prove　that　the　doping　of　Fe　not　only　raises　the　density　of　oxygen　vacancies　but　also　promotes　the　redox　ability　and　oxygen　activity　of　the　catalyst.　We　conducted　in　situ　DRIFTS　(diffuse　reflection　infrared　Fourier　transform　spectroscopy)　experiments　and　density　functional　theory　(DFT)　calculations　to　disclose　the　reaction　mechanism　of　H2S　oxidation.　The　derived　insights　are　important　for　the　design　of　efficient　ceria-related　catalysts　for　practical　applications.　©　2020　American　Chemical　Society.