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. © 2014 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.