The Mo¨ssbauer spectra of the system (PbTiO3)0.95(BiFeO3)0.05have been studied from room temperature to 585°C. From the isomer‐shift of 0.491±0.02 mmsec−1at room temperature, the ionicity is found to be 60%±20%. A discontinuity in the plot of isomer‐shift versus temperature atTcis observed. The quadrupole splitting at room temperature is 0.295±0.02 mm/sec−1. A dip in the Mo¨ssbauer fraction is observed at the Curie temperature.