Phosphorus-doped carbon nanospheres without any metal residues were synthesized and characterized.The results revealed that the doping phosphorus atoms could significantly improve the electrocatalytic activity of graphitic carbon for the oxygen-reduction reaction (ORR) both in acidic and alkaline media,and the materials exhibited high electrocatalytic activity,long-term stability,and excellent tolerance to crossover effects especially in alkaline media.Quantum mechanics calculations with the density functional theory demonstrated that the changes in charge density and energetic characteristics of frontier orbitals for the P-doped graphene sheet could facilitate the ORR.