Polyacrylonitrile (PAN) based carbon nanofibers were prepared by electrospinning and their activity for oxygen reduction reaction (ORR) in acidic media was investigated. Field emission electron microscope (FE-SEM), transition electron microscope (TEM), X-ray photoelectron spectroscopy (XPS) and cyclic voltammetry (CV) were carried out to investigate the surface morphology, composition, and catalytic activity. Thin carbon nanofibers of a 150 nm diameter were successfully produced by electrospinning using 8 wt% PAN in dimethylformamide, 15 cm pin to plate distance, and applying voltage of 18 kV at different carbonization temperatures of 700, 900, 1000, 1100, and 1200 °C. The ORR activity of the prepared carbon nanofibers was evaluated. The PAN based carbon nanofibers showed a considerable ORR activity and this activity was increased by increasing the carbonization temperature. The high ORR onset potentials over 700 mV vs. RHE (milli-volt versus reversible hydrogen electrode) were obtained at temperatures over 1000 °C. The activity of PAN based carbon nanofibers increased with increasing carbonization temperature from 700 to 1100 °C, this would be related to the increasing in the electrical conductivity at low carbonization temperatures, and the high Pyridine N content at the high carbonization temperatures.