A family of iron perovskites with the general formula AFeO3-δ (A = Ln1-xMx; Ln = La, Nd and/or Pr; M = Sr or/and Ca) has been prepared keeping fixed the A cation radius 〈rA〉 and cation size mismatch to isolate the effect of divalent dopant concentration from the A-cation steric effects. The electrochemical behaviour of these compounds for their application as SOFC cathodes was evaluated by using I-V curve measurements and ac impedance spectroscopy over three electrodes electrolyte supported cells processed under identical conditions. In contrast with the bulk behaviour, trends are more difficult to observe due to microstructural effects, but results seem to indicate that the doping level, x, does not influence in a significant way the electrochemical performance of iron perovskites with identical 〈rA〉 and σ2(rA). © 2009 Elsevier B.V. All rights reserved.