Perovskite LaMnO3 is reported to be a superior electrocatalyst for oxygen reduction reaction in terms of the onset potential and intrinsic activity. However, traditionally prepared LaMnO3 is characterized to exhibit a low specific surface area and a limited pore volume. Herein, we synthesize a three-dimensional ordered macroporous LaMnO3 that features ordered and interconnected porous structure, in order to increase catalytic sites. The obtained three-dimensional ordered macroporous LaMnO3 exhibits an increased specific surface area of 20.328 m2 g−1 and pore volume of 0.126 cm3 g−1. Rotating-ring-disk electrode measurement reveals a more positive onset potential (0.827 V) and half-wave potential (0.686 V), and a much higher current-limited density (5.90 mA cm−2) of the three-dimensional ordered macroporous LaMnO3 compared to counterparts, as well as a high electron transfer number (∼4) and a better stability. Furthermore, a LiO2 battery employing the three-dimensional ordered macroporous LaMnO3 as air electrode exhibits excellent electrochemical performance with a higher initial discharge capacity (5592 mAh g−1), a smaller discharge-charge voltage gap (1.56 V), and a higher coulombic efficiency (∼100%) in comparison with the carbon electrode. Our results suggest that traditional perovskite oxides could be effectively optimized for efficient electrocatalytic reactions.