A controllable Co doping strategy is introduced to significantly activate more catalytic sites for Mn-based materials and anchor Co-Mn nanoparticles on the N-doped carbon nanotube (N-CNT) substrates. The as-synthesized CoMn2O4/N-CNTs exhibit excellent ORR catalytic performance with large limited current density and positive half-wave potential, even outperforming the Pt/C catalysts. The outstanding ORR activity allows the CoMn2O4/N-CNTs to directly serve as the cathode electrode in a liquid/solid state Zn-air battery, demonstrating large power density and robust stability.