The aim of this work is to study the changes in the chemical composition of a commercial impregnating coal-tar pitch due to the thermal treatment, using whole samples and the corresponding single isotropic phases and mesophases separated by hot filtration. A deeper knowledge of the molecular size and structure of the components present in the samples was achieved by means of size exclusion chromatography (SEC), planar chromatrography (PC), UVfluorescence (UV-F), solid and solution-state 13 C NMR and MALDI-mass spectrometry. The results showed that during thermal treatment there is not only a change in the relative amounts of different molecular size compounds but also in the characteristics of the compounds in each SEC fraction which increase in size with increasing treatment. The study of the single isotropic phases and mesophases yielded some interesting results, which were correlated with the different molecular structure of the compounds present in each phase.