Fine and uniform La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3−δ powder was synthesized by a glycine-nitrate combustion process. La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3−δ electrodes were prepared on dense Ce 0.8 Sm 0.2 O 2−δ electrolyte substrates using a spin-coating technique by sintering at 900-1,000°C. The electrode properties of La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3−δ were investigated by electrochemical impedance spectroscopy and chronopotentiometry techniques with respect to preparation conditions and the resulting microstructures. The results indicate a significant effect of the microstructure on the electrode processes and polarization characteristics. The oxygen adsorption and dissociation process acted as a larger contribution to the overall electrode polarization R p in magnitude compared with the charge transfer process due to relatively low porosity levels of the electrodes. It was detected that the grain size of the electrodes exhibited a crucial role on the electrocatalytic reactivity. At 800°C, the electrode sintered at 950°C attained a polarization resistance of 0.18 Ω cm 2 , an overpotential of 27 mV at a current density of 200 mA cm −2 , and an exchange current density of 308 mA cm −2 .