Liquid-liquid equilibria of multicomponent systems involved in the synthesis of glycerol carbonate from dimethyl carbonate and glycerol were experimentally measured. Particularly, data for the ternary systems dimethyl carbonate + methanol+ glycerol and dimethyl carbonate + glycerol carbonate + glycerol and the quaternary system dimethyl carbonate + methanol + glycerol carbonate + glycerol are provided at 333.2 K, 338.2 K and 343.2 K at atmospheric pressure since these temperatures prove relevant for the synthesis of carbonate glycerol from glycerol and dimethyl carbonate. The experimental data obtained were correlated with a good degree of agreement to the NRTL model in order to obtain the corresponding binary interaction parameters. (C) 2014 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.