BiFeO3 ceramics was synthesized by solid state reaction technique. Synchrotron X-ray diffraction analysis was employed to investigate the phase formation and structure determination. Rietveld refinement of the diffracted data confirmed the rhombohedrally distorted perovskite structure with space group R3c. Localized atomic structure determined from fitted X-ray data showed off centered displacement of Fe3+ cations with a magnitude of 0.397 angstrom along c-axis. The FeO6 octahedron comprised of two types of Fe-O bonds with bond lengths of similar to 1.935 angstrom and similar to 2.131 angstrom Impedance spectroscopic data collected in wide temperature (300-400 K) and frequency (200 Hz-2 MHz) ranges, demonstrated two relaxation phenomena corresponding to two heterogeneous phases. The best fits to the collected impedance data were achieved by employing an equivalent circuit model R-g(RgbCgb)(R(e)Q(e)). Grain boundaries showed only p-type small polaronic hopping conduction process assisted with the oxidation of Fe3+ to Fe4+ in measured temperature range of 300-400 K. Grains exhibited p-type small polaronic hopping conduction mechanism up to 375 K; however, above 375 K electronic conduction becomes prominent. Conduction is dominated by short range hopping of the polarons among Fe3+ and Fe4+ or through the first ionized oxygen vacancy bridge between Fe3+ and Fe2+ cations. (C) 2013 Elsevier B.V. All rights reserved.