The electrochemical performance and microstructure stability of PrBaCo2O5+delta (PBCO) cathode are investigated in CO2-containing atmospheres for solid oxide fuel cells (SOFCs). Electrochemical impedance spectra results confirm obvious performance degradation of the PBCO cathodes in the presence of CO2 impurity, especially in high CO2 concentration condition. Microstructure and structural analyses reveal the formation of insulating BaCO3 nanoparticles at the PBCO surface, which is considered as the primary reason for the loss of electrode activity. This study highlights the important role of surface segregated BaO species in determining the activity and long-time stability of PBCO electrode. (C) 2017 Elsevier B.V. All rights reserved.