Highly active and stable electrocatalysts are mandatory for developing high-performance and long-lasting fuel cells. The current study demonstrates a high oxygen reduction reaction (ORR) electrocatalytic activity of a novel spinel-structured LaFe₂O₄ via a self-doping strategy. The LaFe₂O₄ demonstrates excellent ORR activity in a protonic ceramic fuel cell (PCFC) at temperature range of 350–500 °C. The high ORR activity of LaFe₂O₄ is mainly attributed to the facile release of oxide and proton ions, and improved synergistic incorporation abilities associated with interplay of multivalent Fe³⁺/Fe²⁺ and La³⁺ ions. Using LaFe₂O₄ as cathode over proton conducting BaZr_0.4Ce_0.4Y_0.2O₃ (BZCY) electrolyte, the fuel cell has delivered a high-power density of 806 mW/cm² operating at 500 °C. Different spectroscopic and calculations methods such as UV–visible, Raman, X-ray photoelectron spectroscopy and density functional theory (DFT) calculations were performed to screen the potential application of LaFe₂O₄ as cathode. This study would help in developing functional cobalt-free ORR electrocatalysts for low temperature-PCFCs (LT-PCFCs) and solid oxide fuel cells (SOFCs) applications.