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The work deals with the study of the phase and structural behaviour of the rare-earth substituted BiFeO3. X-ray powder diffraction examinations revealed that the polar R3c phase in the Bi1-xRExFeO 3 systems with RE = Er, Tm and Yb do not exceed 7, 4 and 3 mol.% of rare earth, respectively. Partial substitution of Er and Tm for the Bi sites in BiFeO3 reduce the temperature of the ferroelectric phase transition R3c-Pbnm on 30-60 K. © 2012 IEEE.