In situ X-ray diffraction has been used to investigate the phase stability of barium strontium cobalt iron oxide (BSCF) with the formula Ba0.5Sr0.5Fe1-xCoxO3-delta (X = 0, 0.2, 0.4, 0.6, 0.8, and 1). The thermal decomposition processes in both low partial pressures of oxygen (air-10(-5) atm pO(2)) and in reducing conditions have been detailed. BSCF manifests excellent stability down to 10(-5) atin pO(2); however, it decomposes through a complex series of oxides under reducing conditions. Increasing the cobalt content results in a decrease in the temperature range of stability of the material under 4% H-2 in N-2, with the initial decomposition taking place at 375, 425, 550, 600, 650 and 675 degrees C, for x = 1, 0.8, 0.6, 0.4, 0.2 and 0, respectively. Further, the thermal expansion is a strong function of the oxygen activity and Co content. The x = 0, 1 end member, BSC, undergoes a phase transition from rhombohedral to cubic symmetry at similar to 800 degrees C under 10(-5) atm pO(2), resulting in an ideal perovskite with a = 3.9892(3) angstrom at room temperature. (C) 2008 Elsevier Inc. All rights reserved.