In this paper, we have investigated the role of phosphorus (P) in nitrogen (N) and phosphorus dual-doped carbon electrocatalyst for oxygen reduction reaction (ORR) in alkaline media with three samples prepared by varying the doping orders of N and P. Results show that the resultant N-POMC (first doped with P, then N) exhibits an outstanding activity for ORR in alkaline media. The mechanism leading to the improved activity is found to be associated with the orientation effect of the first doped P on the later doped N, by increasing the ratio of graphitic-N significantly. Furthermore, a portion of the first doped P can act as the doping sites and be replaced by the later doped N, called 'self-sacrifice' mode, which is confirmed by both experiments and density functional theory (DFT) calculations. However, this orientation effect cannot be observed in the other two dual-doped samples. In addition, experimental and DFT calculation also prove that the amount of graphitic-N is important in improving the activity for ORR. The doping strategy reported in this work is applicable to various co-doping systems in exploring the synergy effect of different dopants and improving activity for ORR. (C) 2017 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.