Rechargeable lithium–oxygen (Li–O2) battery is one of the most promising technologies among various electrochemical energy storage systems, while the incapability of the electrocatalyst and the inefficient transport of reactants in the O2 electrode still limit the round-trip efficiency, rate capability, and cycle stability of the Li–O2 battery. Here, three-dimensional ordered macroporous LaFeO3 (3DOM-LFO) is synthesized and employed as electrocatalyst in Li–O2 battery with relatively stable TEGDME based electrolyte. The Li–O2 cells with 3DOM-LFO show enhanced electrochemical performances, including low overpotential, high specific capacity, good rate capability and cycle stability up to 124 cycles. This enhanced catalytic performance might be due to the synergistic effect of the porosity and catalytic activity of the 3DOM-LFO catalyst.
