The self-hardening activity of fly ashes was investigated looking for the possibility of their chemical reactions with water without additives. A method had to be developed for separation of the structural water from the adsorbed or free one. The decomposition of the chemically bound water was measured by thermogravimetry. The‘I’ dimensionless number proved to be applicable for the quantitative characterisation of the measured data with more DTG peaks. The examined reaction depends on the chemical composition and the physical structure of the fly ashes and the time of interaction with water. The SO3 content seems important, but the characteristics of the formed compounds differ deeply from the CaSO4·2H2O. The observed and examined reaction is an important factor of the self-hardening process of fly ash deposits.