A two-dimensional Zn-based metal-organic framework has been synthesized by using Zn(II) ions and H2SDC (4,4'-stilbenedicarboxylic acid) under solvothermal conditions. The framework having a trinuclear Zn3-(RCO2)6 SBUs connected by the 4,4'-stilbenedicarboxylic acid to form a hexagonal network, shows a two-dimensional structure and displays high thermal stability up to approximately 330 °C. The role of Zn2+ (from Zn-SDC) for epoxide activation and Br- ion (from TBABr) for ring opening of epoxide was studied for the cycloaddition reaction of CO2 and propylene oxide (PO) under ambient conditions. Zn-SDC was found catalytically efficient towards CO2-epoxide coupling under ambient reaction conditions with high selectivity towards the desired cyclic carbonates under solvent-free conditions. The effects of various reaction parameters such as catalyst loading, temperature, CO2 pressure, and time were evaluated. Zn-SDC was easily separable and reusable at least five times without any considerable loss in the initial activity. A plausible reaction mechanism for the cycloaddition reaction was also proposed based on literature and experimental inferences.