The exploring of catalysts with high‐efficiency and low‐cost for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) is one of the key issues for many renewable energy systems including fuel cells, metal–air batteries, and water splitting. Despite several decades pursuing, bifunctional oxygen catalysts with high catalytic performance at low‐cost, especially the one that could be easily scaled up for mass production are still missing and highly desired. Herein, a hybrid catalyst with NiCo alloy nanoparticles decorated on N‐doped carbon nanofibers is synthesized by a facile electrospinning method and postcalcination treatment. The hybrid catalyst NiCo@N‐C 2 exhibits outstanding ORR and OER catalytic performances, which is even surprisingly superior to the commercial Pt/C and RuO2 catalysts, respectively. The synergetic effects between alloy nanoparticles and the N‐doped carbon fiber are considered as the main contributions for the excellent catalytic activities, which include decreasing the intrinsic and charge transfer resistances, increasing CC, graphitic‐N/pyridinic‐N contents in the hybrid catalyst. This work opens up a new way to fabricate high‐efficient, low‐cost oxygen catalysts with high production. NiCo alloy nanoparticles decorated on N‐doped carbon nanofibers as a highly active and durable oxygen electrocatalyst at low‐cost are synthesized and reported. The hybrid catalyst with suitable amount of NiCo alloy nanoparticles loading (NiCo@N‐C 2) gives the most outstanding oxygen reduction reaction and oxygen evolution reaction electrocatalytic performances, which is even surprisingly superior to the commercial Pt/C and RuO2 catalysts, respectively.