Polycrystalline samples of La0.6Ca0.4Fe1−xNixO3 (x=0.1, 0.2, 0.3) (LCFN) are prepared by liquid mix method. The structure of the polycrystalline powders is analyzed with X-ray powder diffraction data. The XRD patterns are indexed as the orthoferrite similar to that of LaFeO3 having a single phase with orthorhombic perovskite structure (Pnma). The morphological characterization is performed by scanning electron microscopy (SEM) obtaining a mean particle size less than 300nm.Polarization resistance is studied using two different electrolytes: Y-stabilized zirconia (YSZ) and Sm-doped ceria (SDC). Electrochemical impedance spectroscopy (EIS) measurements of LCFN/YSZ/LCFN and LCFN/SDC/LCFN test cells are carried out. These electrochemical experiments are performed at equilibrium from 850°C to room temperature, under both zero dc current intensity and air. The best value of area specific resistance (ASR) obtained is 0.88Ωcm2, corresponding to the La0.6Ca0.4Fe0.9Ni0.1O3 material using SDC as electrolyte. The dc four-probe measurement indicates that La0.6Ca0.4Fe0.9Ni0.1O3 exhibits fairly high electrical conductivity, over 300Scm−1 at T>500°C.