The electronic structural changes of La0.6Sr 0.4CoO3-δ cathodes with oxygen vacancy formation by reducing oxygen partial pressures, p(O2)'s were investigated in detail using X-ray absorption spectroscopy to understand metallic-like electronic conduction mechanism. The oxygen nonstoichiometry of La 0.6Sr0.4CoO3-δ was controlled by annealing the samples under various p(O2)'s and quenched to room temperature. Co K-edge X-ray absorption near edge structure (XANES) spectra revealed that the Co average valence decreased with decreasing p(O2), which was also confirmed by iodometric titration. The Co L-edge XANES spectra were hardly changed with changing p(O2)-s. Meanwhile, the peak area of the O K-edge XANES spectra strongly depended on p(O2). This result revealed the strong hybridization between the O 2p and Co 3d states. It was concluded the introduction of oxygen vacancies narrowed the hybridized orbital of O 2p and Co 3d states, resulted in a decrease in the mobility as well as the concentration of electron holes with decreasing p(O2).