Barium cerate based compounds are promising candidates for construction of different electrochemical devices. Previously published papers were focused on improvement of chemical stability and on increase of protonic conductivity of BaCeO3-based materials. Different approaches: aliovalent doping, formation of solid solutions or modification of synthesis method have been tested in order to develop the optimal material with desired properties. Recently, the concept of the composite material formation was implemented in order to improve the properties of BaCeO3-based protonic ceramic materials. In this work the results concerning the influence of barium phosphate and barium tungstate on the electrical properties of BaCeO3-based materials were presented and discussed. Our previous studies have shown that such modification leads to the improvement of chemical stability. In this work the electrical properties of developed BaCe0.9Y0.1O3-Ba-3(PO4)(2) and BaCe0.9Y0.1O3-BaWO4 composites were determined using Electrochemical Impedance Spectroscopy (EIS). It was found that introduction of barium phosphate into the BaCeO3 leads mainly to modification of grain boundaries, while the introduction of tungstate phase modifies the electrical properties of both bulk and grain boundaries. The discussion concerning the influence of used modifiers on crystallographic structure, microstructure and electrical properties of developed materials and observed correlation is also presented. (C) 2014 Elsevier B.V. All rights reserved.