Exploring efficient metal-free electrocatalysts for oxygen reduction reactions (ORR) will have a great impact on the field of fuel cells and metal-air batteries. In this paper, we report a simple and efficient routine to coat ordered mesoporous carbon (CMK-3) with nitrogen-doped carbon via pyrolysis of the surface-self-polymerized polydopamine. The optimized CMK-3 catalyst with a coating of nitrogen-doped carbon demonstrates excellent electrocatalytic activity towards ORR in alkaline media. The coating procedure under optimized conditions lowers the ORR half-wave-potential by 80 mV, giving a genuine metal-free catalyst with an onset ORR potential of 0.96 V (vs reversible hydrogen electrode (RHE)) and half-wave potential of 0.83 V (vs RHE) in 0.1 M KOH, which is much better than other carbon material-based catalysts (such as carbon nanotubes and their composites). The performance of this surface-nitrogen-rich CMK-3 catalyst is also superior to that of N-doped ordered mesoporous carbon synthesized by means of the 'nanocasting' technique. Furthermore, the as-prepared catalyst performs comparably in terms of activity, superior durability, and higher tolerance to methanol compared with commercially available Pt/C.