The effect of Ba-impregnation within a bi-layered NiO-YSZ/NiO-GDC anode for solid oxide fuel cells (SOFC) has been investigated. The in situ formation of BZY/BCG proton conducting phases is proved by X-ray diffraction (XRD) and analyzed in detail by the Rietveld method. The integration of barium within the cermet microstructure is also evidenced by Electron Microscopy, where the presence of BZY/BCG phases creates possible additional paths for proton conduction. Electrochemical impedance spectroscopy (EIS) analysis indicates that the proton conducting phases generate a global decrease in the total polarization resistance, and in particular in its charge transfer component. (C) 2014 Elsevier B.V. All rights reserved.