Exploring economically efficient electrocatalysts with robust oxygen reduction catalytic activities and developing appropriate structures are necessary to understand fuel cells with high open-circuit voltages and long lifespans. In this work, a high-performance ORR catalyst was prepared with a one-spot method by pyrolysis of a urea, FeCl3, and NaCl mixture. The surface element distribution was studied by XPS etching, showing the active sites ϵ-Fe3N with active Fe–N bonding. Benefiting from the double layer protection, in which the ϵ-Fe3N nanoparticles were covered by an N-doped carbon layer encapsulated in carbon bamboo-like nanotubes, the catalysts showed abnormal stability with 5000 cycles, a negative shift of only 15 mV by the CV test and a 3% attenuation after 60,000 s of operation. The onset potential is found to be 0.96 V, which is a positive shift of 12 mV compared to that of the state-of-the-art Pt/C catalyst. The ORR kinetic analysis indicates that the catalyst shows a Tafel slope of 82 mV decade−1 at high potential and 130 mV decade−1 at low potential close to that of the reference catalyst, suggesting a similar reaction mechanism. Therefore, successfully synthesized nonnoble electrocatalysts offer a novel strategy and promising candidates to promote the further development of clean energy devices.