Oxygen electrocatalysis is a key process for many effective energy conversion techniques, which requires the development of high-performance electrocatalysts. Carbon nanofibers featuring good electronic conductivity, large specific surface area, high axial strength and modulus, and good resistance toward harsh environments have thus been recognized as reinforcements in oxygen electrocatalysis. This review summarizes the recent progress on carbon nanofibers as electrocatalysts for oxygen electrocatalysis, with special focus on the modulation of carbon nanofibers for further elevating their electrocatalytic performance, which includes morphological and structural engineering, surface and pore size distribution, defect engineering, and coupling with other electroactive materials. Additionally, the correlation between the geometrical/electronic structure of their active centers and electrocatalytic activity is systematically discussed. Finally, conclusions and perspectives of this interesting research field are presented, which we hope will provide guidance for the future fabrication of more advanced carbon-fiber-based electrocatalysts.