Fuels　with　extremely　low　sulfur　content　are　highly　desirable　as　a　result　of　the　growing　environmental　concerns.　In　this　work,　a　simple　and　novel　method　to　connect　a　ZrIV　open　site　with　polyoxometalates　(POM)　was　introduced,　which　was　used　as　an　effective　heterogeneous　catalyst　for　oxidative　desulfurization　of　fuel　oil.　ZrPTAX-BTC　composites　were　synthesized　conveniently　and　rapidly　at　room　temperature　and　atmospheric　pressure　using　pyromellitic　acid　(BTC)　as　a　linker.　The　products　were　characterized　by　XRD,　TGA,　FT-IR,　NMR,　SEM,　and　N2　adsorption–desorption,　which　verified　the　successful　preparation　of　ZrPTAX-BTC　composite.　ZrPTAX-BTC　catalyst　has　high　content　of　active　components,　and　has　excellent　catalytic　activity　in　oxidative　desulfurization　reaction.　It　achieves　rapid　and　complete　desulfurization　under　mild　reaction　conditions　(T　=　50　°C,　O/S　=　4,　t　=　30　min,　DBT　removal　rate　reaches　100%).　Further　studies　show　that　the　synergistic　catalysis　of　a　ZrIV　open　site　and　PTA　molecule　is　the　reason　for　its　high　catalytic　activity,　in　which　the　ZrIV　open　site　promotes　the　decomposition　of　H2O2　into　O2·,　PTA　molecules　combine　with　O2·　to　form　peroxytungstate　(W(O2)n),　and　the　close　distance　between　the　ZrIV　open　site　and　PTA　in　ZrPTAX-BTC　allows　H2O2　to　be　efficiently　utilized.　In　addition,　ZrPTAX-BTC　can　be　easily　recovered　and　reused　for　at　least　five　times,　and　only　a　slight　decrease　in　catalytic　activity　has　occurred.　Therefore,　ZrPTAX-BTC　has　high　catalytic　activity,　high　stability,　and　good　reusability,　which　is　a　potential　catalyst　that　can　realize　the　application　of　fuel　ultradeep　desulfurization.　©　2021　American　Chemical　Society