It is critical and challenging for preparing nonprecious metal catalysts with high catalytic performance in fuel cells and metal-air batteries. In this work, we developed an efficient multistep approach to synthesize metal-organic framework (MOF)@Fe-Phen nanotube-derived composite electrocatalyst (CNCo-n@Fe-x), which consisted of N-riched mesoporous carbon nanotubes with high graphitization degree and uniformly distributed active sites (Co, Fe3C, N-C, Fe-Nx, and Co-Nx). Experimental results indicated that the bimetallic doping was superior to a single metal. Benefiting from the unique hierarchical structure and the synergies among the active sites also the high conductivity, as expected, the composite nanotubes exhibited excellent electrochemical performance for oxygen reduction reaction in alkalinity electrolyte, even better than the commercial Pt/C catalyst. More importantly, when used for constructing the air electrode of the Zn-air battery, CNCo-5@Fe-2 nanotubes also displayed high performance.