The present work attempts a detailed investigation of the features of the phase transitions of Na3Fe2(PO4)3 to a state with high ionic conduction. The samples are obtained by the standard method of solid-phase synthesis. The completeness of chemical reaction is monitored by X-ray phase analysis. The thermal properties of Na3Fe2(PO4)3 are investigated by differential-thermal analysis (DTA). Electrophysical measurements are undertaken on ceramic samples in the form of tablets (diameter 6-12 mm, thickness 2-4 mm), with graphite electrodes applied to the end surfaces. The resistance (conduction) is determined from an analysis of impedance hodographs taken in the frequency range 5-5.105 Hz at temperatures 290-600 K.