A composite of Lanthanum manganese oxide-carbon (LaMnO₃/C) has been also synthesized by a facile electrospinning approach followed by controlled heat treatment, in which the carbon form a continuous conductive network connecting the electrocatalyst LaMnO₃ nanoparticles together to facilitate good electrochemical performance. Based on a correlation between theoretical (DFT) and experimental analysis on the effect of the surface atomic arrangement, the electrocatalyst (Mn-terminated LaMnO₃) with uniform Mn surface termination show favourable rechargeability, and good phase and morphology stability in lithium oxygen batteries compared to La rich surface termination. Excellent cycling performance is also demonstrated, in which the terminal voltage is higher than 2.4 V after 100 cycles at limited capacity of 1000 mAh g^-1 (based on composite).