To investigate the role of P in the dual-doped carbon electrocatalyst for oxygen reduction reaction (ORR) in alkaline media, three samples are prepared by varying the doping orders of N and P. Results show the resultant N-POMC (first doped with P, then N) exhibits an outstanding activity for ORR in alkaline media. The reason lies in the orientation effect of the first doped P on the later doped N, by increasing the ratio of graphitic-N significantly, confirmed by our experimental and DFT calculation. In addition, our results prove that the amount of graphitic-N is important in improving the activity for ORR. The doping strategy in this work is applicable to c0-doping strategy in exploring the synergy effect of different dopants and improving activity for ORR.