The　ultra-deep　desulfurization　of　oil　needs　to　be　solved　urgently　due　to　various　problems,　including　environmental　pollution　and　environmental　protection　requirements.　Oxidative　desulfurization　(ODS)　was　considered　to　be　the　most　promising　technology.　The　facile　synthesis　of　highly　efficient　and　stable　HPW-based　heterogeneous　catalysts　for　oxidative　desulfurization　is　still　a　challenging　task.　In　this　paper,　pentamethylene　hexamine　(PEHA)　and　phosphotungstic　acid　(HPW)　were　combined　by　a　simple　one-step　method　to　prepare　a　heterogeneous　catalyst　of　PEHA-HPW　for　the　production　of　ultra-deep　desulfurization　fuel　oil.　The　composite　material　exhibited　excellent　catalytic　activity　and　high　recyclability,　which　could　reach　a　100%　dibenzothiophene　(DBT)　removal　rate　in　30　min　and　be　recycled　at　least　5　times.　Experiments　and　DFT　simulations　were　used　to　better　examine　the　ODS　mechanism　of　PEHA-HPW.　It　was　proved　that　the　rich　amino　groups　on　the　surface　of　PEHA-HPW　play　a　crucial　role.　This　work　provides　a　simple　and　feasible　way　for　the　manufacture　of　efficient　HPW-based　catalysts.　©　2023　The　Chemical　Industry　and　Engineering　Society　of　China,　and　Chemical　Industry　Press　Co.,　Ltd