The surface exchange coefficient and chemical diffusion coefficient of oxygen for the perovskites La0.6Sr0.4Co1–yFeyO3–delta (y=0.2, 0.5 and 0.8) were measured using the conductivity relaxation technique. Measurements were performed between 600 and 800 °C in an oxygen partial pressure range between 10–4 and 1 bar. Both transport coefficients decrease markedly with decreasing oxygen partial pressure below about 10–2 bar at all temperatures. This is attributed to ordering of oxygen vacancies. Implications for using La0.6Sr0.4Co1–yFeyO3–delta as an oxygen separation membrane are discussed.