DTA, TG, XRD and IR methods were used to study the formation of solid solutions in the selected subsolidus range of the PbZrO3-K0.5Bi0.5TiO3 system by heating mixtures prepared using oxide substrates, i.e. PbO, Bi2O3, ZrO2, TiO2 and K2CO3. It was found that solid solutions are formed in the reaction of PbO and ZrO2 with intermediate compound, i.e. K0.5Bi0.5TiO3. PbZrO3 was not found to be formed as an intermediate phase.