In this paper, the electrochemical performance of nanostructured LaNi0.6Fe0.4O3-δ (LNF) infiltrated La2NiO4+δ (LNO) material was evaluated as a potential cathode for BaZr0.1Ce0.7Y0.2O3-δ (BZCY)-based proton-conducting solid oxide fuel cell (H-SOFC). The performance of LNO backbone cathodes with different loading amounts of LNF infiltrated phase were investigated, and electrochemical studies implied that the single cell with about 31 wt% LNF infiltrated cathode exhibited the lowest polarization resistance of 0.027 Ω cm2 and the highest maximum power density of 969 mWcm−2 at 700 °C, which were encouraging compared with that in previous reports of cobalt-free cathodes for H-SOFCs. This work demonstrated that the infiltrated LNF-LNO cathode had a great potential for H-SOFC and the optimization of the loading amount of LNF nanoparticles on LNO was critical for the fuel cell performance.