This work highlights the possibility of the application of YBaCo₄O_7+δ-modified materials as cathodes for solid oxide fuel cells based on protonic electrolytes. To reach this goal, the basic YBaCo₄O_7+δ oxide material and its YBaCo_3.5Zn_0.5O_7+δ (YBCZ) and YBaCo_3.5Fe_0.5O_7+δ (YBCF) substituted members were successfully synthesized and their structural, thermal and electrochemical properties were evaluated for their suitability for application. It was found that the substitution of cobalt with zinc results in the structural stabilization of such “114” phases and the convergence of the thermal expansion coefficient with that of the selected BaCe_0.5Zr_0.3Dy_0.2O_3–δ (BCZD) electrolyte as well as superior electrochemical activity below 700 °C. The Ni-BCZD|BCZD|YBCZ cell yields relatively high power density (200 mW cm^–2 at 600 °C) and exhibits low polarization resistance (0.51 Ω cm² at 600 °C). This, combined with the low activation energy values found for electrode polarization conductivity of both symmetrical and fuel cells allow assuming that the Zn-substituted YBaCo₄O_7+δ material could be successfully used in electrochemical devices based on proton-conducting electrolytes.