A facile and ultrafast microwave-assisted thermolysis approach has been adopted to synthesize hierarchical nitrogen-doped carbon within a very short time. The precursor PANI@carbon felt composite was pyrolyzed in microwave oven for different time (10, 20, 30, 40, 50 s) and denoted as NC-X (X = 10, 20, 30, 40, 50). As for NC-30, nitrogen-doping content is obtained up to 3.62 at% with striking enrichment of pyridinic N as high as 45% of the total nitrogen content. Raman analysis indicates the extent graphitization level for the resultant NC-30 and the relative intensity I D/I G was 1.26. High nitrogen-doping content and graphitization level provide effective active sites and efficient electron transfer channel. The resultant NC-30 exhibits pronounced ORR activity with an onset potential of 0.94 V (versus RHE), half-wave potential of 0.80 V and diffusion limiting current density of -5.23 mA cm-2, comparable to those of the commercial Pt/C. It also shows enhanced stability with current retention of 98.3% over 7.5 h as well as superior tolerance against methanol. The simple preparation and excellent ORR performance of NC-30 suggest its promising practical application.