Although Pt-based catalysts have been considered as the most effective electrocatalyst for the cathodic oxygen reduction reaction (ORR) of direct methanol fuel cells (DMFCs), they still suffer from the drawbacks of high cost, poor long-term stability and methanol/ CO poisoning effects. Thus, developing low-cost ORR catalysts with high efficiency, durability and antipoisoning ability is of paramount importance. Herein, a series of non-noble metal FeNC materials are prepared through a facile pyrolysis process and used as the electrocatalysts toward ORR in alkaline electrolyte. Results show that the Fe_0.50NC-800-1h catalyst pyrolyzed at 800 ºC for 1 h with the mass ratio of Fe(NO₃)₃·6H₂O to melamine being 0.50 exhibits the highest catalytic performance among the as-prepared FeNC catalysts. The half-wave potential of ORR is ca. 0.81 V, which is only 38 mV lower than that on the noble metal Pt/C catalyst. Besides, it also displays higher stability and methanol tolerance than Pt/C. There is almost no change in the current during the chronoamperometric test when methanol is added in the electrolyte whereas significant decrease is found on Pt/C catalyst. This study of FeNC catalysts provides new insights on understanding the ORR mechanism and suggests a promising strategy to develop low-cost and highly efficient non-noble metal electrocatalysts for ORR.