A facile and effective self-catalyzed sucrose combustion was developed to synthesize single-phase BiFeO 3 (BFO) that exhibited unusual ferromagnetic properties. Microscopy techniques were employed to examine morphologies and structures of the BFO. Reaction mechanism of the formation of the BFO was deduced by using thermo-gravimetric analysis and differential scanning calorimetry. Moreover, optical properties of the BFO were investigated by using UV–vis spectroscopy. Both magnetization hysteresis loops and zero field-cooling/field-cooling indicated that BFO had typical characteristics of spin-glass. X-ray photoelectron spectroscopy was used to expose the origin of the magnetism of the sample.