The oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) are considered as the two crucial reactions in key renewable-energy technologies including fuel cells and water splitting. Despite promising research progress in the preparation of various non-noble metal based electrocatalysts, it is still highly challenging but desirable to develop novel fabrication strategies to synthesize highly active and cost-effective ORR/OER bifunctional electrocatalysts in a precisely controlled manner. Herein, we report atomic layer deposition (ALD) of highly monodisperse Co3O4 nanocrystals of different sizes on N-doped electrospun carbon nanofibers (nCNFs) as high performance bifunctional catalysts (Co@nCNFs) for the ORR and OER. Co@nCNFs (with an average Co3O4 particle size of ∼3 nm) show high ORR performance exhibiting an onset potential of 0.87 V with a low Tafel slope of 119 mV dec-1 approaching that of commercial Pt/C. Similarly, the Co@nCNF electrocatalyst showed remarkable catalytic activity in the OER. The turnover frequency (TOF) value determined at an overpotential of 550 mV for the Co@nCNFs is ∼0.14 s-1 which is ca. 3 and ca. 15-fold higher than those of bulk Co (∼0.05 s-1) and the standard state-of-the-art IrOx (0.0089 s-1) catalyst, respectively. This work will open new possibilities for fabrication of inexpensive non-noble metal materials in highly controlled manner for applications as bifunctional ORR/OER electrocatalysis.