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 ΔV = −3 cm3/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.