High pressure polymerization of glycidol was carried out at four different pressures ranging from p = 0.1 MPa up to p = 800 MPa at room temperature (T = 298 K). To monitor polymerization kinetics at high pressure dielectric spectroscopy was employed. Constant rates of polymerization at given thermodynamic conditions were determined form the analysis of dc conductivity as well as variation of the static dielectric permittivity. To be sure that both quantities can be used to monitor progress of the polymerization reaction, complementary FTIR studies were carried out at ambient pressure. The vibration of the C-O-C epoxy rings assigned to the band in the 760-880 cm(-1) range was chosen to follow progress of the monomer conversion. The rate constant "k" determined from the Fourier Transform Infrared data analysis, was found to be in good correlation with dielectric data. Furthermore, having rate constant obtained for polymerization carried out at different pressures and constant temperature the activation volume was determined Delta V = -3 cm(3)/mol. Finally, analysis with the use of MALDI-TOF2 MS2 equipment showed that high pressure favors formation of polymers of greater molecular weight. Moreover, it was found that mechanism of polymerization at high pressure is quite different with respect to the reaction carried out at ambient pressure. It turned out that side reaction occurring upon polymerization of glycidol are completely eliminated at high compression. (c) 2014 Elsevier Ltd. All rights reserved.