The sequence of the solid state reactions in the PbOZrO 2-TiO2-Nb2O5-NiO system has been investigated. The oxide mixing route utilised in sample preparation was selected in order to determine the basic reaction path in the formation of the PZTPNN perovskite phase. It has been established that the main intermediate phases formed prior to PZTPNN are PbTiO3 and pyrochlore Pb-Nb-based phases. The sequence in the pyrochlore formation was from tetragonal Pb3Nb2O8 (500 °C) to rhombohedral Pb2Nb2O7 (600-750 °C) and finally to cubic Pb3Nb4O13 (650-850 °C). The formation of the perovskite phase proceeded from mutual solubility of PbTiO3 and pyrochlore Pb3Nb4O13 phases, accompanied by dissolving of residuals (PbZrO3 and NiO) in the perovskite solid solution formed