Abstract Highly crystalline BiFeO₃ (BFO), Bi_0.97Sm_0.03FeO₃ (Sm-BFO) and BiFe_0.97Co_0.03O₃ (Co-BFO) nanoparticles (NPs) were utilized as potential magnetic hyperthermia agents at two different frequencies in the radiofrequency (RF) range, and the effect of Sm³⁺ and Co²⁺ ion doping on the physical properties of the material was examined. The thermal behaviour of the as-prepared powders disclosed that the crystallization temperature of the powders is affected by the incorporation of the dopants into the BFO lattice and the Curie transition temperature is decreased upon doping. Vibrational analysis confirmed the formation of the R3c phase in all compounds through the characteristic FT-IR absorbance bands assigned to O–Fe–O bending vibration and Fe–O stretching of the octahedral FeO₆ group in the perovskite, as well as through Raman spectroscopy. The shift of the Raman-active phonon modes in Sm-BFO and Co-BFO NPs indicated structural distortion of the BFO lattice, which resulted in increased local polarization and enhanced visible light absorption. The aqueous dispersion of Co-BFO NPs showed the highest magnetic hyperthermia performance at 30 mT/765 kHz, entering the therapeutic temperature window for cancer treatment, whereas the heating efficiency of all samples was increased with increasing frequency from 375 to 765 kHz, making our doped nanoparticles to be suitable candidates for potential biomedical applications.