Nano-crystalline (BaTiO3)(0.95) - (LaFeO3)(0.05) (BTO-LFO5%) solid solution was synthesized using sol-gel method. X-ray diffraction (XRD) measurements show that BTO-LFO5% ceramics crystallize in a tetragonal structure. Impedance relaxation was studied in large windows of frequency and temperature. The electrical properties were found to be significantly dependent on temperature. From Cole-Cole (Nyquist) plots, we demonstrate that the grain bulk and grain boundaries are responsible for the conduction regime at high temperature (T > T-C). The grain bulk and grain boundary activation energies were determined using impedance and modulus spectroscopy. The activation energy magnitudes indicate that the conduction mechanism could be attributed to structural defects and charge carriers. (c) 2017 Elsevier B.V. All rights reserved.