A low cost, durable, and efficient electrocatalyst for oxygen reduction reactions (ORR) is essential for high-performance fuel cells. Here, we fabricated Co3O4 nanoparticles (NPs) anchored on N-doped mesoporous carbon nanofibers (Co3O4/NMCF) by electrospinning combined with the simple heat treatment. Within this composite, carbon nanofibers possess a mesoporous structure, contributed to obtain a high surface area, which can facilitate the infiltration of electrolyte. Moreover, this one-dimensional (1D) carbon nanofiber also acts as a 1D conductive channel, effectively improving the transmission of electrons. In addition, the doping of the N element with high content combined with homogenously distributed Co3O4 NPs can significantly enhance the ORR electrocatalytic activity. Benefiting from the advantages of material and structure, the Co3O4/NMCF catalyst favors a four electron transfer process in alkaline media, exhibiting good ORR electrocatalytic activity, and its durability is much better than that of commercial Pt/C.