At the porous $La_{0.6}Ca_{0.4}MnO_{3-{delta}}$(LCM)/YSZ electrodes of solid oxide fuel cells (SOFC), the electrochemical redox reaction of oxygen proceeds via the triple boundary (TPB) of gas/LCM/YSZ. The surface diffusion of adsorbed oxygen on LCM has been proposed as the rate determining process, assuming the gradient of oxygen chemical potential from the outer surface of porous layer to TPB. Along with the formation of this gradient, oxygen nonstoichiometry in the bulk of LCM may varies. In this paper, an electrochemical technique was described precisely to determine the variation of oxygen content in LCM of porous LCM/YSZ under polarization. It was shown that the oxygen potential in LCM layer under large cathodic polarization is much lower than that in the gas phase, being determined from the electrode potential and Nernst equation.