In this work, three unique structured Co, N-codoped carbon catalysts (hollowed-out octahedral, yolk-shell and peanut-like) have been synthesized. The structures of the three Co, N-codoped carbon catalysts are shown in Fig. 1. Electrochemical tests show the three catalysts exhibit high ORR performance in alkaline medium, including a high onset potential and half-wave potential, four-electron reduction process, excellent methanol crossover resistance and long-term stability. The high surface area, sufficient Co-Nx and graphitic N active sites and suitable pore structure make a synergetic contribution to improving the ORR performance of the three catalysts. The features such as the high ORR performance, low-cost raw materials and simple synthetic approach, make the three Co, N-codoped carbon catalysts available to be promising non-noble metal cathodic catalysts for alkaline fuel cells.