Naturally occurring phyllosilicate minerals such as talc and vermiculite in conjunction with n-tetra butyl ammonium bromide (TBAB) co-catalyst were found to be efficient in the coupling of CO2 with epoxides to form cyclic carbonates. The reaction was carried out in a pressurized autoclave reactor at moderate pressures of 10–35 bars and temperatures of 100–150 °C. The optimized catalyst system exhibited > 90% conversion of the epoxides and > 90% selectivity for the desired cyclic carbonates, in the presence or absence of a solvent. The selectivity of the catalytic system could be improved with heat pre-treatment of the phyllosilicates albeit this resulted in slightly lower epoxide conversion. The results obtained using the heat treated phyllosilicates strongly support the hydrogen bond assisted mechanism for the cycloaddition of epoxides and CO2. The cycloaddition reaction could also be carried out in the absence of TBAB, although lower cyclic carbonate yields were observed. The phyllosilicate part of the catalyst system is heterogeneous, easy to separate after completion of reactions and reusable a number of runs without loss of activity.