An efficient Zn(Bmic)(AT) MOF with available Lewis acid-base blocks was prepared by a solvothermal method combining the mixed ligands 5-aminotetrazole (HAT) and 1-benzimidazole-5-carboxylic acid (H(2)Bmic). The prepared Zn(Bmic)(AT) catalyst is rich in amino groups, uncoordinated oxygen atoms, and multiple open metal sites (OMSs), which contribute to CO2 adsorption of 79 cm(3)/g at 273 K and 52 cm(3)/g at 298 K, with high adsorption enthalpy (28 kJ mol(-1)). Furthermore, its multiple functional sites facilitate CO2 cycloaddition to various small-molecule epoxides to give five-ring cyclic carbonates with the assistance of a Bu4NBr cocatalyst, achieving a high TON of 170 for propylene carbonates (PC) under solvent-free, mild conditions (80 degrees C, 5 bar). In addition, the Zn(Bmic)(AT) catalyst exhibits good recyclability for six consecutive cycles. Moreover, a feasible synergistic mechanism of Zn(Bmic)(AT)/Bu4NBr catalysts for CO2 conversion into cyclic carbonate is proposed.