La_0.7Sr_0.3CoO_3−δ (LSC) powder was characterized by thermogravimetry. Thin, dense layers of LSC were deposited by RF magnetron sputtering on YSZ pellets. The electrochemical behavior was studied as functions of temperature (300–530°C) and oxygen partial pressure (0.21–2×10⁻⁵ bar) by impedance spectroscopy. Impedance diagrams were decomposed into two elements, characteristic of the electrode polarization. The low frequency contribution can be described either as a limiting Warburg diffusion loop or as a semi-circle. These results can be interpreted in terms of a progressive evolution of the limiting process as functions of oxygen pressure and temperature, i.e. a finite diffusion process in series with dissociative sorption process. Under low oxygen pressure, at temperatures higher than 475°C, gas-phase diffusion polarization becomes significant.