The catalytic activity of both ZIF-8 and Zr/ZIF-8 has been investigated for the synthesis of chloromethyl ethylene carbonate (CMEC) using carbon dioxide (CO2) and epichlorohydrin (ECH) under solvent-free conditions. Published results from literature have highlighted the weak thermal, chemical, and mechanical stability of ZIF-8 catalyst, which has limited its large-scale industrial applications. The synthesis of novel Zr/ZIF-8 catalyst for cycloaddition reaction of ECH and CO2 to produce CMEC has provided a remarkable reinforcement to this weak functionality, which is a significant contribution to knowledge in the field of green and sustainable engineering. The enhancement in the catalytic activity of Zr in Zr/ZIF-8 can be attributed to the acidity/basicity characteristics of the catalyst. The comparison of the catalytic performance of the two catalysts has been drawn based on the effect of different reaction conditions such as temperature, CO2 pressure, catalyst loading, reaction time, stirring speed, and catalyst reusability studies. Zr/ZIF-8 has been assessed as a suitable heterogeneous catalyst outperforming the catalytic activities of ZIF-8 catalyst with respect to conversion of ECH, selectivity and yield of CMEC. At optimum conditions, the experimental results for direct synthesis of CMEC agree well with similar literature on Zr/MOF catalytic performance, where the conversion of ECH, selectivity and the yield of CMEC are 93%, 86%, and 76%, respectively.