Exploring　eco-friendly　and　cost-effective　strategies　for　structure　engineering　at　the　nanoscale　is　important　for　boosting　heterogeneous　catalysis　but　still　under　a　long-standing　challenge.　Herein,　multifunctional　polyphenol　tannic　acid,　a　low-cost　natural　biomass　containing　catechol　and　galloyl　species,　was　employed　as　a　green　reducing　agent,　chelating　agent,　and　stabilizer　to　prepare　Au　nanoparticles,　which　were　dispersed　on　different-shaped　CeO2　supports　(e.g.,　rod,　flower,　cube,　and　octahedral).　Systematic　characterizations　revealed　that　Au/CeO2-rod　had　the　highest　oxygen　vacancy　density　and　Ce(iii)　proportion,　favoring　the　dispersion　and　stabilization　of　the　metal　active　sites.　Using　isopropanol　as　a　hydrogen-transfer　reagent,　deep　insights　into　the　structure-activity　relationship　of　the　Au/CeO2　catalysts　with　various　morphologies　of　CeO2　in　the　catalytic　nitrobenzene　transfer　hydrogenation　reaction　were　gained.　Notably,　the　catalytic　performance　followed　the　order:　Au/CeO2-rod　(110),　(100),　(111)　＞　Au/CeO2-flower　(100),　(111)　＞　Au/CeO2-cube　(100)　＞　Au/CeO2-octa　(111).　Au/CeO2-rod　displayed　the　highest　conversion　of　100%　nitrobenzene　and　excellent　stability　under　optimal　conditions.　Moreover,　DFT　calculations　indicated　that　nitrobenzene　molecules　had　a　suitable　adsorption　energy　and　better　isopropanol　dehydrogenation　capacity　on　the　Au/CeO2　(110)　surface.　A　reaction　pathway　and　the　synergistic　catalytic　mechanism　for　catalytic　nitrobenzene　transfer　hydrogenation　are　proposed　based　on　the　results.　This　work　demonstrates　that　CeO2　structure　engineering　is　an　efficient　strategy　for　fabricating　advanced　and　environmentally　benign　materials　for　nitrobenzene　hydrogenation.　©　2023　The　Royal　Society　of　Chemistry