Composite electrode materials were successfully obtained by mixing of PrBaCo2O6–δ (PBCO) and Ca3Co4O9±δ (CCO) oxides. No interactions between the components under long term sintering and SOFC's operating conditions were evidenced by means of x-ray diffraction analysis. Increase of CCO content is shown to contribute to the perceptible decline in thermal expansion coefficients in the background of a negligible decrease in electrical conductivity of ceramics. The obtained powdered composites are shown to possess a developed microstructure and an excellent adhesion with Ce0.8Sm0.2O1.9 dense support. Low values of polarization resistances equal 0.28 and 0.69 Ω∙cm2 at 873 K were achieved for compositions with 70% and 50% of the PBCO phase, respectively. The distribution relaxation times (DRT) method was implemented to reveal the rate-limiting steps of the electrochemical reaction. The applying of CCO as TEC lowering admixture to PBCO instead ceria-based oxides was demonstrated to be more effective approach.