A systematic study on copper(II) as catalyst for the synthesis of glycerol carbonate via oxidative carbonylation is here reported for the first time. Copper(II) chloride has been found to efficiently promote the process under homogeneous conditions treating glycerol with CO:O-2 (P-tot = 4 MPa; P-(02) = 0.7 MPa), in DMA at 130 degrees C and in the presence of pyridine as co-catalyst. Excellent conversions (>92%) and selectivities (>93%) are obtained in relatively short reaction times (3-4h) also with copper(II) complexes. The catalyst overall TON is evaluated and new experimental evidences are provided allowing significant advancements in the mechanism comprehension. (C) 2013 Elsevier B.V. All rights reserved.