Incorporation　of　ionic　liquids　into　metal-organic　frameworks　(MOFs)　offers　a　new　platform　to　construct　heterogeneous　bifunctional　catalytic　systems　for　the　chemical　capture　and　conversion　of　CO2　with　epoxides.　Herein,　an　imidazolium-based　ionic　liquid　decorated　UiO-66　type　MOF　(P3[BCMIm]Br@UiO-66)　was　successfully　constructed　via　solvothermal　assembly　of　the　carboxyl-functionalized　imidazolium　ionic　liquid　ligand,　terephthalic　acid　ligand　and　Zr(iv)　ions.　It　exhibits　the　highest　catalytic　activity　upon　the　cycloaddition　of　CO2　(98.2%　conversion　of　propylene　oxide　and　99%　selectivity　to　propylene　carbonate)　under　optimized　conditions　(2.2　Mpa　CO2,　1.0　wt%,　110　°C,　reaction　time　2　h).　Notably,　P3[BCMIm]Br@UiO-66　outperformed　the　original　UiO-66　materials　and　[BCMIm]Br.　P3[BCMIm]Br@UiO-66　retained　its　good　catalytic　performance　for　up　to　five　recycling　runs　with　only　a　little　loss　in　catalytic　activity.　Furthermore,　several　additional　coupling　reactions　were　investigated　with　other　epoxides　as　substrates.　©　2024　The　Royal　Society　of　Chemistry.