The transesterification of dimethyl carbonate (DMC) with glycerol to produce glycerol carbonate was investigated in the presence of CaO under various reaction conditions. CaO was completely dissolved in the reaction mixture of glycerol and DMC in 5 min at 75 degrees C and at the molar ratio of glycerol/DMC/CaO of 1/2/0.01. The isolation and the characterization of the dissolved Ca species by means of TOF-SIMS, elemental analysis, and FT-IR revealed that an active species, Ca(C3H7O3)(OCO2CH3) is generated from the interaction of CaO with glycerol and DMC. The mechanistic pathways to the formations of Ca(C3H7O3)(OCO2CH3) and glycerol carbonate are discussed on the basis of experimental and spectroscopic results. (C) 2011 Elsevier B.V. All rights reserved.