The direct synthesis of tungsten nitride (WN) nanoparticles on nitrogen-doped carbon black (N-carbon black) was achieved through facile nucleation and growth of WN nanoparticles on simultaneously generated N-carbon black under ammonia annealing. As a noble-metal-free catalyst, the WN/N-carbon black hybrid exhibited excellent performance in ORR, coupled with superior methanol tolerance and long-term stability in comparison to commercial Pt/C catalysts, through an efficient four-electron-dominant ORR process.