Efficient electrocatalyst for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) is the most critical factor to influence the performance of lithium–air batteries. We present La0.8Sr0.2MnO3 (LSM) perovskite nanorods as high active electrocatalyst fabricated via a soft template method for lithium–air batteries. The as–prepared LSM nanorods are microporous with numerous defects and large surface area (20.6 m2 g−1), beneficial to the ORR and OER in the discharge and charge processes, respectively. Lithium–air batteries based on the microporous LSM nanorods electrocatalysts show enhanced electrochemical performances, including high first discharge specific capacity (6890 mAh g−1 (electrode) at 200 mA g−1), low overpotential, good rate capability (up to 400 mA g−1), and cycle stability (only 1.1% voltage loss after 30 circles of specific capacity limit of 1000 mAh g−1 tested at 200 mA g−1). The improved performance might be due to the synergistic effect of the unique microporous and one–dimensional structure and numerous defects of the prepared LSM catalyst.