Nanofibers with unique structures and multiple components have attracted more and more attention, which could combine multi-functions in one entity. Janus-type biphasic nanofibers with unique structure can be quickly obtained by electrospinning technology. We produced CoO x /C nanofibers with Janus structure by self-made side-by-side electrospinning spinneret, combined with electrospinning technology and heat treatment. CoO x /C nanofibers had a large amount of graphitic carbon distributed on one half of the Janus nanofiber, and CoO x /C nanoparticles were embedded in the other half of the Janus nanofiber and distributed uniformly. CoO x /C acted as ORR catalysis, and graphitic carbon, pridinc-N and CoO x in CoO x /C had a synergistic effect on their catalytic activity. The results confirmed that CoO x /C was dominated by four-electron pathway under alkaline conditions, and the Tafel slope was lower than that of commercial Pt/C catalysts. The preparation method of this work is simple and easy, the structure is controllable, and the composition is adjustable, which provides a feasible way for preparing Janus structure nanofibers with different functions.