The paper presents the studies on determination of physicochemical and structural properties of hydrothermally treated (HTT) silica gel Si-60, using the differential scanning calorimetry (DSC) and N2 adsorption methods. Modification was performed in overheated water vapours or under the liquid water layer using various sources of thermal energy (in the classical autoclave or in the high-pressure microwave reactor). The characteristics of porous structure were determined on the basis of low-temperature nitrogen adsorption/desorption isotherms and using the calorimetric data (DSC) of thermal effects of phase transition of water introduced inside pores of the studied materials. Great compatibility of the characteristics obtained by means of the above-mentioned methods was proved. As follows from the SEM analysis, during HTT silica is rebuilt resulting in great changes of surface morphology and porous structure of the materials. The range of these changes depends on both the applied system (water vapour/liquid water) and the kind of used energy (classical/microwave).