Gas-tight perovskite La_0.6Sr_0.4Co_0.2Fe_0.8O_3-δ(LSCF)oxygen transport membranes were prepared by supersonic air-gas plasma spraying (SAPS) and low pressure plasma spraying-physical vapor deposition (PS-PVD). Surface exchange and bulk diffusion of the oxygen species of the two membranes were compared by the use of O₂-TPD and XPS. The O₂-TPD result shows the desorptions of the physical, chemical adsorbed oxygen and the lattic oxygen of the SAPS membrane were 2, 3 and 6 times respectively more than those of the PS-PVD membrane. The XPS result also shows a higher proportion of adsorbed oxygen of the SAPS membrane than that of the PS-PVD membrane. All the above results demonstrate that the SAPS membrane should has better adsorption and dissocation abilities on oxygen, and should also possesses more intrinsic oxygen vacancies and higher capacity of vancancy formation.