Bismuth ferrite (BiFeO3), a perovskite material, rich in properties and with wide functionality, has had a marked impact on the field of multiferroics, as evidenced by the hundreds of articles published annually over the past 10 years. Studies from the very early stages and particularly those on polycrystalline BiFeO3 ceramics have been faced with difficulties in the preparation of the perovskite free of secondary phases. In this review, we begin by summarizing the major processing issues and clarifying the thermodynamic and kinetic origins of the formation and stabilization of the frequently observed secondary, nonperovskite phases, such as Bi25FeO39 and Bi2Fe4O9. The second part then focuses on the electrical and electromechanical properties of BiFeO3, including the electrical conductivity, dielectric permittivity, high-field polarization, and strain response, as well as the weak-field piezoelectric properties. We attempt to establish a link between these properties and address, in particular, the macroscopic response of the ceramics under an external field in terms of the dynamic interaction between the pinning centers (e.g., charged defects) and the ferroelectric/ferroelastic domain walls.