a b s t r a c tFive different compositions of brownmillerite materials, Ce-and La-doped, and undoped Ba 2 In 2 O 5 were synthesized via the solid-state reaction and the glycine-nitrate combustion process. Properties of the materials were characterized using XRD, HR-TEM, and TGA/DSC techniques. Conductivity measurements by AC impedance spectroscopy, performed in air and hydrogen-containing atmospheres, in the temperature range from 100• C to 500• C, were correlated to the properties of the materials and revealed the effects of dopant, microstructure, temperature and atmosphere on the total electrical conductivity of the materials. All compositions showed low conductivity in air. In hydrogen-containing atmospheres, while Ce-and La-doped Ba 2 In 2 O 5 showed low conductivity (4 × 10 −6 -3 × 10 −6 S cm −1 at 500 • C), undoped Ba 2 In 2 O 5 demonstrated a surprisingly high conductivity (between 0.02 S cm −1 and 0.7 S cm −1 in the temperature range from 300• C to 500• C), especially samples produced by the glycine-nitrate process. This finding creates potential opportunity for using Ba 2 In 2 O 5 as a proton-conductive material in intermediate temperature fuel cells.