In this paper, a statistical analysis with response surface methodology (RSM) has been used to investigate and optimize process variables for the greener synthesis of chloromethyl ethylene carbonate (CMEC) by carbon dioxide (CO2) and epichlorohydrin (ECH). Using the design expert software, a quadratic model was developed to study the interactions effect between four independent variables and the reaction responses. The adequacy of the model was validated by correlation between the experimental and predicted values of the responses using an analysis of variance (ANOVA) method. The proposed Box-Behnken design (BBD) method suggested 29 runs for data acquisition and modelling the response surface. The optimum reaction conditions of 353 K, 11 bar CO2 pressure, and 12 h using fresh 12% (w/w) Zr/ZIF-8 catalyst loading produced 93% conversion of ECH and 68% yield of CMEC. It was concluded that the predicted and experimental values are in excellent agreement with ±1.55% and ±1.54% relative errors from experimental results for both the conversion of ECH and CMEC yield, respectively. Therefore, statistical modelling using RSM can be used as a reliable prediction technique for system optimization for greener synthesis of chloromethyl ethylene carbonate via CO2 utilization.