Glycerol carbonate is a key bifunctional compound employed as solvent, additive, monomer, and chemical intermediate. We have synthesized it on a pilot scale in the laboratory in cyclic or alicyclic organic carbonate medium. In this study, we examined the use of supercritical CO2 as a reaction medium and as a source of carbonate for carbonatation of glycerol. Glycerol carbonate could be obtained by direct reaction of carbon dioxide with an organic carbonate in the presence of heterogeneous catalysts. Carbonatation of glycerol into glycerol carbonate went to equilibrium in supercritical CO2 medium.