[(CH3)(2)NH2][Co-3(BTC)(HCOO)(4)(H2O)]H2O (Co-BTC) was synthesized under solvothermal conditions, further used as the precursor for the synthesis of 2-methylimidazole modified Co-BTC (2MeIm@Co-BTC-x). The characteristics of 2MeIm@Co-BTC-x were systematically characterized by various technologies including XRD, FESEM, FT-IR, XPS, N-2-adsorption, TG-DTG and CO2/NH3-TPD. It was found that except for the crystal faces (0 1 1) and (-1 0 2) corresponding to ZIF-67 and Co-BTC, a new crystal phase appeared at 12.22(o) for the modified Co-BTC, which may be attributed to the coordination between 2MeIm and unsaturated Co ions of Co-BTC. Interestingly, a new structure of hexagonal prisms together with hierarchical porous were also formed for the modified Co-BTC. Besides, when this composite was explored as a heterogeneous catalyst for catalytic conversion of carbon dioxide with epichlorohydrin (ECH) as probe, an obvious enhancement in catalytic activity was obtained compared with the fresh Co-BTC, suggesting that 2MeIm ligands within the modified Co-BTC played a great role on the coupling process. Furthermore, 97.21% of ECH conversion and 98.79% of chloropropene carbonate selectivity were gained over [email protected] under optimal conditions (3.0MPa, 90 degrees C, 5h, 0.75wt% catalyst of ECH). Additionally, only a slight decrease in catalytic activity was found after the optimal sample was reused three times. Finally, a mechanism for interpreting the coupling process of carbon dioxide cycloaddition with epoxide was proposed.Graphic AbstractOne-pot catalytic conversion of CO2 into cyclic carbonate over 2-methylimidazole modified Co-BTC [GRAPHICS] .