PrBaFe2O6–δ (PBF) is considered as a promising material for mixed ionic-electronic conductors used in high-temperature applications. In the present work, PBF was used as a basis for two chemical modification approaches, including doping with cobalt, nickel and copper, as well as composite design with the addition of a BaCe0.8Sm0.2O3–δ phase. The single-phase and composite materials were successfully prepared and characterized in terms of their functional properties. The two approaches were found to synergistically affect the functional properties of PBF, allowing a trade-off between thermomechanical and transport properties to be achieved. As a result, the prepared 70 wt% PrBaFe1.9M0.1O6–δ (M = Co, Ni, Cu) + 30 wt% BaCe0.8Sm0.2O3–δ composites exhibit acceptable electrochemical activity in the intermediate-temperature range. The best electrochemical activity was found for the sample with M = Cu, whose polarization resistance at 700 °C reaches 1.7 Ω cm2. Therefore, the designed PBF-based composites can be considered as promising electrode materials for solid oxide fuel cell applications. © 2024 Elsevier Ltd.