Developing cost-effective and stable Pt-free electrocatalysts for the oxygen reduction reaction (ORR) is now the key issue for the large-scale application of zinc-air batteries. Here, we present a simple charge modulation strategy to synthesize Co 2+ -activated spinel CoMn 2 O 4 supported self-catalysis derived nitrogen-doped carbon nanotubes (CoMn 2 O 4 /NCNTs@Ni). Associated with the formation of high valence Mn 3.4+ over the octahedral site of CoMn 2 O 4 , the corresponding oxygen binding energy can be effectively tuned to greatly enhance the activity of ORR, further revealed by the density functional theory calculations. Benefiting from the highly conductive CoMn 2 O 4 -NCNTs-Ni electron transport channels and high valence Mn 3.4+ , the CoMn 2 O 4 /NCNTs@Ni catalyst exhibits excellent oxygen electrocatalytic activity (the limiting-current density was 5.51 mA cm −2 ) and stability (the current density remained at 86.80% within 24 h), with much lower ORR overpotentials than Mn 3 O 4 /NCNTs@Ni (the limiting-current density was 5.35 mA cm −2 and the current density remained at 71.63% within 13 h). The as-obtained CoMn 2 O 4 /NCNTs@Ni as a cathode can further assemble a zinc-air battery, which delivers an open-circuit potential of 1.46 V, even close to that of Pt/C (1.50 V), and excellent stability (charge-discharge stably for 238 h). This charge modulation strategy provides a new way to design and explore highly active, durable, and cost-effective catalysts for renewable energy conversion and storage. The optimized CoMn 2 O 4 /NCNTs@Ni with high valence Mn 3.4+ as the catalytic site center, combined with the spinel-NCNTs-Ni electron transport channels jointly promote the electrocatalytic activity and successfully applied in zinc-air battery.