The main purpose of the present paper is to distinguish water located in various types of pores contained within cement paste. The water sorption isotherm is the starting point of the experimental analysis. The investigation was conducted employing the conventional gravimetric method on cement paste composed with w/c=0.5. The investigation was conducted for the following relative humidity values: 11%, 54%, 75%, 84%, 93%, 97% and 100%. Once samples reached the equilibrium water content they were investigated by means of differential scanning calorimetry (DSC), which enabled us to record exothermic peaks corresponding to the crystallization of different water portions. Moreover, we intended to investigate the thermodynamic characteristics of the liquid phase confined within cementitious materials. Hence, the artificial pore solution was prepared. In order to determine the phase transition temperature and the amount of formed ice, the solution was used to saturate silica gel, which is a chemically passive material. Then the thermal analysis was conducted.