A series of cyclic voltammetry, chronoamperometry and electrochemical impedance experiments have been carried out in order to investigate the effect of cathode composition and porosity on the electrochemical characteristics of strontium-doped lanthanum, praseodymium and gadolinium cobaltite cathodes. The impedance responses at different electrode potentials of the half cell and symmetric single cell setups are compared and analyzed by the equivalent circuit modeling method. The deconvolution of impedance spectra for single cell cathode and anode reactions contributions based on the results of simultaneous analysis of half cells and symmetric single cells has been made by differential impedance real part vs. ac frequency plot analysis method. Noticeable influence of cathode chemical composition, meso-porosiiy and macro-porosity on the electrochemical activity of the oxygen electroreduction has been demonstrated. Seeming activation energy values have been calculated and discussed. (C) 2009 Elsevier Ltd. All rights reserved.