AbstractRechargeable non-aqueous lithium-oxygen batteries with a large theoretical capacity are emerging as a high-energy electrochemical device for sustainable energy strategy. Despite many efforts made to understand the fundamental Li-O₂ electrochemistry, the kinetic process of cathodic reactions, associated with the formation and decomposition of a solid Li₂O₂ phase during charging and discharging, remains debate. Here we report direct visualization of the charge/discharge reactions on a gold cathode in a non-aqueous lithium-oxygen micro-battery using liquid-cell aberration-corrected scanning transmission electron microscopy (STEM) combining with synchronized electrochemical measurements. The real-time and real-space characterization by time-resolved STEM reveals the electrochemical correspondence of discharge/charge overpotentials to the nucleation, growth and decomposition of Li₂O₂ at a constant current density. The nano-scale operando observations would enrich our knowledge on the underlying reaction mechanisms of lithium-oxygen batteries during round-trip discharging and charging and shed lights on the strategies in improving the performances of lithium-oxygen batteries by tailoring the cathodic reactions.