AbstractBrownmillerite-perovskite intergrowths of the type m(A2B2O5)*n(ABO3), where m = 1 and n = 1, were investigated with respect to cation ordering. It was found that Sr31n2ZrO8, Sr31n2HfO8, Ba3Sc2TiO8 and Ba31n2TiO8 form in a disordered cubic structure, while Sr3Sc2ZrO8 and Ba3Sc2ZrO8 form an ordered cation arrangement. The Arrhenius plots of the oxygen ion conductivity of Ba3Sc2ZrO8, Sr31n2HfO8, and Ba31n2TiO8 contain discontinuities that appear to be caused by an oxygen vacancy order-disorder transition. High temperature powder-X ray diffraction did not show any evidence for cation ordering that might otherwise have created the changes in activation energy in the conductivity plots.