The insufficient electrocatalytic activity and CO2 resistance hinder the application of cathode material for solid oxide fuel cells (SOFCs). In this study, we introduce a series of Pr-doped perovskite Bi0.8–xPrxCa0.2FeO3–δ (BPCFx, x=0, 0.10, 0.15, 0.20) as candidate cathode materials, with a focus on its phase structure, oxygen desorption ability, catalytic activity, and electrochemical reduction kinetics. Among all the components, the Bi0.6Pr0.2Ca0.2FeO3–δ (BPCF0.20) catalyst shows impressive oxygen reduction reaction (ORR) activity, with a low polarization resistance of 0.06 Ω cm2 at 700 °C and peak power density of 810 mW cm−2 at 800 °C. Moreover, the BPCF0.20 cathode shows outstanding CO2 resistance in different CO2 concentrations (1%–10%) due to the larger average bond energy and higher relative acidity of Bi, Pr, and Fe ions. These findings demonstrate that BPCFx are advanced cathode electrocatalysts for SOFCs.