As the core part of Al-air batteries cathode, the catalytic performance of electrocatalyst affects the industrialization process of Al-air batteries. In this work, nitrogen-doped carbon material (N/VC2) was prepared through urea high temperature treatment method based on commercial Vulcan-72XC carbon material. Mn3O4@N/VC2, MnO@N/VC2 and MnO2@N/VC2 composites were further obtained by loading different manganese oxides. MnO2@N/VC2 displays the superior oxyen reduction reaction (ORR) performence with the positive onset potential of 0.872 V. In addition, Al-air battery based on MnO2@N/VC2 shows excellent discharge performance in high current density, and the maximum power density can reach 136 mW·cm-2. The interaction between carbon carrier and manganese oxide was studied by comparing the electrocatalytic properties of different composites. The results show that the synergistic action of porous structure and abundant defect sites is the main reason for improving the catalytic activity of the material. This work provides a theoretical basis for the research and development of manganese-based oxide catalysts.