In recent times, perovskite oxides have recognized to be an ideal alternative to platinum-based oxygen reduction reaction (ORR) electrocatalysts due to their excellent stability, cost-effectiveness, and tailorable properties. Herein, an ABO3 type LaFeO3 perovskite was doped at its B-site to form electrochemically active LaFeB′O6 (B′=Cr, Zn, Co) by one-pot hydrothermal synthesis process. Due to the synergistic effects of increased surface area and electrochemically active sites, Cr-doped LaFeO3 largely improves the mass transfer kinetics for ORR in both conditions, alkaline (0.1 M KOH) and acidic (0.5 M H2SO4) with a positive onset Eon of 0.80 and 0.81 V (vs Ag/AgCl). Similarly, a half-wave (E1/2) potential of 0.68 and 0.63 V (vs Ag/AgCl), which was comparable to the commercial 20 % Pt/C. Moreover, the La-based perovskites were able to catalyze ORR with an electron transfer number (n)>3.6 signifying the superior 4-electron pathway. Doped and undoped LaFeO3 exhibited remarkable stability in the chronoamperometry studies with a relative current of 92–95 % sustained over 8 h. Additionally, the La-based electrocatalysts was unaffected by the crossover effect of methanol in both acidic and basic conditions, contrary to the commercial 20 % Pt/C. The present work serves as a useful strategy to maximize the efficiency and reliability in perovskites for energy-related electrocatalytic applications and for alternative fuel generation. © 2024 Wiley-VCH GmbH.
