Abstract Highly efficient and non-precious catalysts are imperative for oxygen reduction reaction (ORR) to replace Pt/C. Anchoring efficient active species to carbon supports is a promising and scalable strategy. Here we synthesize Cu nanoparticles and noncrystalline CuNxCy species co-decorated ketjenblack (KB) carbon catalyst (denoted as Cu-N-KB-acid) by a facile and scalable method using copper sulfate, melamine, and KB as raw materials. An initial one-pot hydrothermal treatment is designed before pyrolysis process to achieve the good distribution of Cu and melamine on KB via a possible chelation effect. Owing to the synergistic effect of Cu and CuNxCy on KB, this composite catalyst displays excellent ORR catalytic activity in alkaline solution, which is comparable to the commercial 20% Pt/C. When used as a catalyst in a home-made Al–air battery, it shows a stable discharge voltage of 1.47 V at a discharge density of 50 mA cm−2, a little higher than that of Pt/C (1.45 V).