Metal-organic　frameworks　(MOFs)　exhibit　excellent　structural　properties,　but　their　application　in　catalysis　is　limited　due　to　their　saturated　coordination　structures.　Herein,　catalysts　containing　unsaturated　coordination　MOF　structural　units　loaded　onto　3-aminophenol-formaldehyde　resin　(APF)　were　prepared　using　a　stepwise　assembly　method.　The　amino　groups　in　APF　serve　as　anchoring　groups,　enabling　the　optimal　dispersion　of　zinc　on　the　surface　of　the　carrier.　The　coordination　saturation　and　the　dominant　surface　groups　can　be　controlled　by　the　stepwise　assembly.　SEM,　FT-IR,　UV　spectroscopy,　XPS,　zeta　potential,　and　SAXS　were　employed　to　demonstrate　the　stepwise　assembly　process.　The　characterization　results　revealed　that　the　binding　strength　between　zinc　and　ligands　on　the　APF　spheres,　as　well　as　the　coordination　saturation　state　of　zinc,　progressively　increased　during　the　stepwise　assembly　process.　Additionally,　comprehensive　evaluation　of　the　catalytic　performance　was　conducted　via　the　cycloaddition　reaction　of　CO₂　with　epoxides　to　elucidate　the　feasibility　and　superiority　of　the　synergistic　catalysis　between　metal　ions　and　functional　ligands　in　the　dual-active-center　catalyst.　The　hybrid　catalyst　Zn-BDC/A-1　with　the　highest　surface　roughness　but　lowest　Zn　coordination　exhibited　the　most　efficient　catalytic　performance.　Furthermore,　the　density　functional　theory　(DFT)　calculations　substantiated　that　zinc　centers　on　the　APF　surface　exhibit　a　preferential　coordination　geometry　involving　no　more　than　two　ligand　groups,　and　a　ligand-dominated　chemical　environment.　These　findings　demonstrate　that　the　stepwise　assembly　maintains　the　coordinative　unsaturation　of　metal　centers　and　also　optimizes　the　spatial　availability　of　ligand　functionalities.　©　2025　Elsevier　B.V.