Cu-N-C electrocatalyst was successfully prepared with Cu-BTC and polyacrylonitrile as templates by electrospinning and in-situ growth method. The effect of various N -doped content on the electrochemical performance of the catalyst were investigated and the Cu-N-C-0.25 exhibited the best OER/ORR catalytic activities. When it was applied to the cathode of the zinc-air batteries, the power density of Cu-N-C-0.25 was 209.1 mW cm − 2 , which exceeded that of the commercial Pt/C + IrO2 hybrid catalyst (157 mW cm − 2 ). The excellent electrochemical performance may be attributed to large number of active sites and high specific surface area on Cu-N-C electrocatalyst. It will be a promising alternative to precious metal catalysts containing Pt, Ir or Ru and their oxides. A simple and convenient method (electrospinning technique and soaking technique) was used to prepare a novel Cu-N-CNFs as a bifunctional electrochemical catalyst. The morphology and structure of Cu-N-C-0.25 were studied by SEM. The results showed the conjunct effects of the 3D porous cross-linked microstructures of carbon nanofibers, copper particles, doping of N element and structural defects as catalytic active sites, so that the carbon nanofibers have higher catalytic efficiency. [ABSTRACT FROM AUTHOR]