X-ray diffraction pattern of LaFeO3 synthesized by the combustion method reveals the pervoskite type of the material. Synthesized material has crystallite size of 28-63 nm. Characterization techniques such as X-Ray diffraction studies, scanning electron microscopy, etc., were employed to study morphology and the average particle size, phase and composition of the material. The effect of constituent phase variation on the dielectric, resistivity and impedance properties was examined. The dielectric dispersion with frequency has been explained on the basis of an electron–hole hopping mechanism which is responsible for conduction and polarization. From the ac conductivity study, it is confirmed that the conduction in the present material is of small polaron type. Such materials may be useful to fabricate the interconnecting materials for the solar cell, gas sensors, gas transducers, optoelectronic devices, etc.