Powders of the system (1–x)Bi0.5Na0.5TiO3–xBiFeO3 (x = 0, 0.02, 0.08, 0.10) are synthesized by the combustion reaction method. The crystal structure and the particle size of Bi0.5Na0.5TiO3 are modified by the incorporation of BiFeO3, as can be seen from the infrared spectroscopy and X-ray diffraction results. The inclusion of iron and the increase in the molar percentage of bismuth in the BNT matrix generate new bonds with a different force constant. The structural analysis showed that the addition of BFO to the BNT does not induce any structural phase transition, preserving the rhombohedral symmetry of the Bi0.5Na0.5TiO3 system. The electrical measurements show that the incorporation of iron increases the conductivity of the system generated by an increase in the concentration of oxygen vacancies; alternatively, the addition of 10% of BiFeO3 generates ferrimagnetic behavior reflected in the magnetic hysteresis curves obtained at room temperature.