Mn/Fe Co-doped <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"> <mml:mrow> <mml:msub> <mml:mtext>LaCoO</mml:mtext> <mml:mrow> <mml:mn>3</mml:mn> <mml:mo>−</mml:mo> <mml:mi>δ</mml:mi> </mml:mrow> </mml:msub> </mml:mrow> </mml:math> perovskite

Abstract Perovskite oxides are promising bifunctional electrocatalysts for oxygen reduction reaction and oxygen evolution reaction (ORR/OER). Here, a cooperative Mn–Fe–Co B-site modulation strategy is implemented in LaCoO 3− δ , combined with a low-temperature combustion synthesis that stabilizes a highly defective oxygen sublattice while preserving single-phase crystallinity. A series of LaCoO 3− δ –based perovskites (LMCO, LMFCO244, LMFCO334 and LMFCO) were prepared, among which LMFCO calcined at 700 °C (LMFCO-700) delivered the highest activity. When applied in a zinc–air battery, LMFCO-700 delivers an open-circuit voltage of 1.48 V, a peak power density of 179 mW cm −2 , and remarkable rechargeability over 540 h (1620 cycles) with a high specific capacity of 793 mA g Zn −1 . Mechanism analysis indicates that the Mn–Fe co-doping promotes a favourable redistribution of B-site valence states by increasing the proportion of Mn 4+ and Co 2+ species and stabilizing oxygen vacancies. This coupled Mn 4+ –Co 2+ redox modulation enhances oxygen-intermediate adsorption and accelerates ORR/OER kinetics. The low-temperature synthesis further increases the surface area (11.23 m 2 g −1 ), exposing more accessible active sites. The synergistic electronic, structural and defect modulation achieved here provides a rational pathway for designing high-performance perovskite electrocatalysts for metal–air batteries and related energy-conversion systems.