Oxygen diffusivities and surface exchange coefficients in various porous mullite/zirconia composites were measured at oxygen partial pressures ranging from 20.2 to 2.02 kPa using the conductivity relaxation method. However, the oxygen diffusivities in porous high-zirconia composites could not be determined because of the predominant surface exchange reaction. Oxygen diffusivities and surface exchange coefficients in low-zirconia composites increased with the zirconia content, while the surface exchange coefficients in high-zirconia composites were approximately constant. A percolation threshold of the surface exchange coefficients occured at ∼40 vol% zirconia for porous zirconia/mullite composites. The oxygen diffusivities in porous low-zirconia composites were independent of the oxygen partial pressure, implying that oxygen diffusion in these composites was related to the migration of oxygen vacancies, whose concentration was independent of the oxygen partial pressure. The surface exchange coefficients of high-zirconia composites decreased with increasing oxygen partial pressure. Finally, it was inferred that the rate-limiting step for oxygen surface exchange could be the charge-transfer process.