The　effectiveness　of　the　catalytic　oxidative　desulfurization　(CODS)　process　crucially　depends　on　the　catalytic　activity　of　the　catalyst　and　the　utilization　of　oxidizing　agent.　Catalyst　with　multiple　active　sites　is　an　effective　method　to　improve　the　CODS　effectiveness.　The　Zr(IV)　and　-COOH-containing　metal-organic　framework,　UiO-66-(COOH)(2),　was　synthesized　and　used　as　an　active　and　recyclable　catalyst　for　CODS.　The　UiO-66-(COOH)(2)　shows　higher　catalytic　activity　and　H2O2　utilization　in　the　CODS　process　than　UiO-66/-COOH,　UiO-66,　and　H2BDC.　And　the　high　catalytic　performance　is　derived　from　the　synergistic　effect　between　the　Zr(IV)　open　site　and　free　-COOH　functionality　within　the　framework.　Experimental　analysis　and　DFT　calculations　results　indicate　that　the　synergistic　effect,　which　changes　the　reaction　path　and　protects　the　*O-2(-)　radical,　is　a　very　effective　strategy　to　promote　desulfurization　efficiency　and　the　utilization　efficiency　of　H2O2.　In　addition,　it　is　essential　to　highlight　that　the　active-site　distance　also　has　a　significant　influence　on　the　effectiveness　of　CODS.　This　research　may　provide　a　new　avenue　for　improving　the　CODS　performance.　(C)　2022　The　Korean　Society　of　Industrial　and　Engineering　Chemistry.　Published　by　Elsevier　B.V.　All　rights　reserved.