A process can be used for preparing cyclic carbonates with an exocyclic vinylidene group by reacting a propargylic alcohol with CO2 in the presence of a silver catalyst having at least one bulky ligand a lipophilic carboxylate ligand. After completion of the reaction, the catalyst is separated from the cyclic carbonate by the use of two organic solvents of different polarity and having a miscibility gap. The silver catalyst is enriched in the less polar solvent and the cyclic carbonate in the more polar solvent.