An efficient catalytic system of a zinc cluster and tetrabutylammonium iodide (TBAI) was developed for cyclic carbonate synthesis from epoxides and carbon dioxide (CO₂) without the use of any organic solvents under very mild conditions (25 °C, 1 atm), even in the presence of impurities such as water and air. Electrophilicity of the central Zn(II) ion, the number of trifluoromethyl groups, nucleophilicity and leaving ability of the anion of alkylammonium salts, and various reaction parameters have a great effect on the catalytic activity of the bifunctional catalyst. Therefore, this solvent-free process represents an environmentally friendly example for the catalytic conversion of CO₂ into value-added chemicals and also has the potential to contribute towards decreasing atmospheric CO₂ emission from the burning of fossil fuels.