Potassium peroxotitanate was synthesized by the peroxo method. During the thermal decomposition K2Ti2O5 can be obtained. The isothermal conditions for decomposition of K2[Ti2(O2)2(OH)6]3H2O were determined on the base of DTA, TG and DSC results. DTA and TG curves were recorded in the temperature range 20 and 900C at a heating rate of 10C min–1. The obtained intermediate compounds were characterized by means of quantitative analysis and IR spectroscopy. The mechanism of thermal decomposition of K2[Ti2(O2)2(OH)6]3H2O to K2Ti2O5 was studied. The optimal conditions for obtaining K2Ti2O5 were determined (770C for 10 h).