The　development　of　catalysts　with　excellent　performance　in　oxidative　desulfurization　(ODS)　at　room　temperature　will　greatly　facilitate　the　advancement　of　desulfurization　technology.　An　efficient　novel　strategy,　4-aminopyridine　molecular　bridging　combined　with　manual　grinding,　was　presented　to　encapsulate　HPW　into　UiO-66　for　achieving　stable　loading　of　PW　and　to　produce　abundant　defects　that　contribute　to　the　formation　of　active　complexes　with　strong　oxidation　ability.　The　prepared　catalyst　showed　outstanding　catalytic　activity　in　the　ODS　system,　achieving　full　desulfurization　in　15　min　at　room　temperature　and　a　low　O/S　molar　ratio.　Further　investigations　reveal　that　the　synergistic　catalytic　effect　of　the　faulty　UiO-66　and　PW　is　mostly　responsible　for　superior　catalytic　performance.　UiO-66　rich　in　defects　promote　the　decomposition　of　H2O2　into　radicals,　and　PW　can　combine　with　the　radicals　to　form　more　stable　active　peroxide　intermediates,　then　exerting　the　catalytic　ability　of　ODS　at　room　temperature.　Such　a　synergistic　catalytic　mechanism　provides　a　guide　to　improving　the　oxidation　ability　of　PW-based　catalysts　at　room　temperature.