The transport parameters of La0.6Sr0.4Co0.6Fe0.4O3−δ were determined by electrical conductivity relaxation and high temperature coulometric titration experiments. The experimental response curves were analyzed in the frequency domain. The results obtained by both methods were in good agreement. The chemical diffusion coefficients measured at temperatures of 923–1255 K and oxygen partial pressures of 0.03–1 bar O2, vary between 10−6–5×10−5 cm2 s−1. The experimental activation energies are in the range 95–117 kJ mol−1. At oxygen partial pressures below 0.03 bar O2 the re-equilibration process is completely governed by the rate of oxygen exchange at the interface. The surface exchange coefficients were determined by conductivity relaxation experiments at temperatures of 1000–1285 K and oxygen pressures of 10−4–0.1 bar O2. The activation energy is about 60–70 kJ mol−1. The exchange coefficients are almost proportional to the oxygen pressure. Treatment of the surface in a nitric acid solution for several hours increases the surface exchange rates by factors of 3–5.