In this work, nickel oxide nanofibers (NiO-NFs) are produced by electrospinning method and calcination in air for 5 h. The thermal gravimetric analysis (TGA), field-emission scanning electron microscopy (FE-SEM), fourier transform infrared (FT-IR), X-ray diffraction (XRD), energy dispersive X-ray spectroscopy (EDS), and electrochemical impedance spectroscopy (EIS) are used for characterization of the NiO-NFs. The FE-SEM images of the precursor indicate that a large quantity of nanofibers with diameters ranging from 100-150 nm with tens of micrometers in length can be acquired. Also, the results show that rough NiO-NFs having large specific surface area are composed of the small nanoparticles. After calcination, the nanofibers are composed of cubic structure. The EIS study shows that the value of charge-transfer resistance of the NiO-NFs modified carbon paste electrode (NiO-NFs/CPE) is much smaller than that CPE, indicating a faster electron-transfer process. The NiO-NFs are used as potential catalysts for electro-catalytic oxidation of ethylene glycol (EG) in 0.2 M NaOH solution. The results demonstrate that the NiO-NFs/CPE reveals good electro-catalytic activity towards EG oxidation, showing a suitable stability and robustness.