The suitable structural design of carbon catalysts is a straightforward strategy to achieve a superior electrocatalytic activity for the oxygen reduction reaction. Herein, we firstly design a three-dimensional sphere-and-flake-structured Cu, N co-doped carbon catalyst, via a template-free method, for robust oxygen reduction reaction. The nanostructure is composed of graphene-like nanosheets and carbon nanospheres with abundant mesopores, which can expose numerous active sites. Cu 2 + and the copolymer of PANI and Cu 2 + and melamine play important roles in the construction of the sphere-and-flake structure. By optimizing the addition of melamine, the structure of the catalyst can be successfully controlled. The as-constructed GCNS10 material possesses a large amount of Cu-N x sites and exhibits an excellent electrocatalytic activity for the oxygen reduction reaction, delivering a limiting current density (6.14 mA cm À 2 at À 0.1 V) and stability superior to those of commercial Pt/C materials in 0.1 M KOH solution. These satisfactory performances suggest that GCNS10 is promising as a next-generation non-noble-metal oxygen reduction reaction catalyst. Besides, using an air cathode with the GCNS10 catalyst works well in a Zn-air battery, indicating that GCNS10 can be used in such devices.