The effect of Fe substitution for Co on the thermodynamic and electrical properties of the double perovskites, PrBaCo2-xFexO5+delta (PBCF, x = 0, 0.5, 1), are investigated as cathode materials for intermediate-temperature solid oxide fuel cells (IT-SOFCs). At a given temperature, the electrical conductivity decreases with increasing Fe content, x, in the PBCF-YSZ composites in air. PBCF-YSZ (x = 1) composite appear to be more stable than PBCF-YSZ (x = 0) composite down to lower oxygen partial pressure, p(O-2), at the same temperature. The higher oxidation enthalpies of the x = 1 composite can also explain the superior stability at roughly the same p(O-2). The high entropy change for the x =1 composite can indicate the high probability in the formation of interstitial oxygen at approximately the same p(O-2). Impedance spectra of symmetrical cells (PBCF-YSZ/YSZ/PBCF-YSZ) show lower cathode polarization losses with increasing amounts of Fe. The maximum power densities of x = 0 composite and x = 0.5 composite are 0.68 and 0.72 W cm(-2), respectively, at 973 K. The maximum power density of the x = 1 composite is, however, about 20% higher than that of the other composites. Considering redox stability and electrochemical performance, higher Fe content of PrBaCo2-xFexO5+delta (x = 1) is more suitable as a cathode material than x = 0 composite in IT-SOFC application. Crown Copyright (C) 2011 Published by Elsevier B.V. All rights reserved.