Microwave irradiation of glycerol carbonate allows formation of glycidol, which readily polymerizes to form polyglycerol under mild conditions comparatively to the classical polyetherification reaction involving high temperature and basic conditions. Analysis of the crude reactional mixture indicated the presence of low-molecular weight oligomers constituted mainly of di, tri, and tetraglycerols with small quantities of higher molecular weights oligomers. Molecular size distribution was relatively similar to that of polyglycerols obtained under basic condition, even if these latter contained slightly higher amounts of high-molecular weight oligomers. Structure of oligomers differs slightly according to the conditions of polymerization, and polyglycerols are obtained under microwave activation containing higher contents of cyclic isomers, whereas polyglycerols obtained under basic conditions contain more ramified isomers. (C) 2010 Wiley Periodicals, Inc. J Appl Polym Sci 120: 2354-2360, 2011