The　conversion　of　H2S　to　high-value-added　products　is　appealing　for　alleviating　environmental　pollution　and　realizing　resource　utilization.　Herein,　we　report　the　reduction　of　nitrobenzene　to　aniline　using　waste　H2S　as　a　“hydrogen　donor”　over　the　catalyst　of　FeCeO2−δ　with　abundant　oxygen　vacancies　(Ov),　especially　an　asymmetric　oxygen　vacancy　(ASOv).　The　electron-rich　nature　of　the　ASOv　sites　facilitates　electron　transfer　to　the　electron-deficient　nitro　group,　promoting　the　adsorption　and　activation　of　Ph-NO2　through　the　elongation　and　cleavage　of　the　N-O　bond.　Benefiting　from　the　formation　of　abundant　ASOv　sites,　the　resulting　FeCeO2−δ　achieves　an　impressive　85.6%　Ph-NO2　conversion　and　81.9%　Ph-NH2　selectivity　at　1.5　MPa　and　90　°C,　which　surpasses　that　of　pure　CeO2　with　flower　and　rod　morphologies.　In　situ　FT-IR　measurements　combined　with　density　functional　theory　calculations　have　elucidated　a　plausible　reaction　mechanism　and　a　rate-limiting　step　in　the　hydrogenation　of　Ph-NO2　by　H2S.　©　2024　American　Chemical　Society.