A perovskite-type phase of Bismuth Ferrite, BiFeO3, powder was synthesized by a solid-state reaction via a rapid vibro-milling technique. The effect of calcination condition on the phase formation, and characterization of BiFeO3 powder was investigated. The formation of the BiFeO3 phase investigated as a function of calcination conditions by TG–DTA and XRD. Morphology, particle size and chemical composition have been determined via a combination of SEM and EDX techniques and vibrating sample magnetometer (VSM) were used to characterize the structures and magnetic properties of prepared samples. The rapid vibro-milling is employed for the first time in this work as a significant time-saving method to obtain single-phase BiFeO3 powders.